CN105792947A - Multilayer coating film forming method - Google Patents

Multilayer coating film forming method Download PDF

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Publication number
CN105792947A
CN105792947A CN201480064924.6A CN201480064924A CN105792947A CN 105792947 A CN105792947 A CN 105792947A CN 201480064924 A CN201480064924 A CN 201480064924A CN 105792947 A CN105792947 A CN 105792947A
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acid
hydroxyl
mass
resin
methyl
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CN105792947B (en
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古泽智
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Kansai Paint Co Ltd
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Kansai Paint Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4263—Polycondensates having carboxylic or carbonic ester groups in the main chain containing carboxylic acid groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/57—Three layers or more the last layer being a clear coat
    • B05D7/572—Three layers or more the last layer being a clear coat all layers being cured or baked together
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • C—CHEMISTRY; METALLURGY
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
    • C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
    • C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8093—Compounds containing active methylene groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2401/00—Form of the coating product, e.g. solution, water dispersion, powders or the like
    • B05D2401/20—Aqueous dispersion or solution
    • 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
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09D169/00—Coating compositions based on polycarbonates; Coating compositions based on derivatives of polycarbonates
    • 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
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    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)

Abstract

Provided is a multilayer coating film forming method involving, in order, a step for coating a specific aqueous first pigmented coating material (X), a specific aqueous second pigmented coating material (Y), and a specific clear coating material (Z) which are coated onto an object to be coated that contains a metal material and a plastic material, and a step for curing these three coating films simultaneously. This multilayer coating film forming method is characterized in that, at wavelengths 360-420nm, the average light transmittance of a cured coating film 5[mu]m thick obtained by coating and curing the aqueous first pigmented coating (X) is less than 1%.

Description

Method of forming layered coating film
Technical field
(cross reference of association area)
The application advocates the interests of the priority of the Japanese Patent Application 2013-255844 description (it is entirely through being incorporated herein by reference) in December in 2013 submission on the 11st.
The present invention relates to the method for forming layered coating film of a kind of film being formed and no matter being respectively provided with the chipping resistance of excellence, tack, retouching, weatherability and ethanol petrol resistant relative to metal parts or plastic components.
Background technology
Generally, car body has the plastic components such as the metal parts forming vehicle body and bumper.
In the application of this car body, conventional widely used following operation: utilize the different coating being suitable to all parts such as metal parts and plastic components and different coating process to carry out application, then, plastic components is installed on metal parts.
But, in recent years, in order to reduce equipment cost in the manufacturing process of car body with to make metal parts consistent with the tone of plastic components, seek a kind of method of application when plastic components being installed on metal parts.
The such as coating process of a kind of body of a motor car being assembled with acrylic resin parts on metal foil disclosed in patent documentation 1.
But, middle painting coating disclosed in patent documentation 1 does not have electric conductivity, it is therefore necessary to polypropylene member application conductive primers coating.In other words, in patent documentation 1, to polypropylene member application conductive primers successively coating → middle painting coating → painting coating, to metal parts successively application are coated with coating → painting coating.It is to say, owing to being not that plastic components is carried out application all of identical coating with identical coating process with metal parts, therefore cost reduce consistent with tone in insufficient.
A kind of water-based paint compositions containing specific anionic property urethane resin emulsion and specific urethane resin is had disclosed in patent documentation 2.But, when by this paint spraying in metal parts and plastic components, even if chipping resistance and light transmittance are no problem, the tack that certainly can not be compared to plastic components with waterborne conductive priming paint mutually is abundant.
A kind of water-borne primer coating composition containing water polyolefin system resin (A), the water-base resin (B) of at least one in waterborne polyurethane resin and water-borne acrylic resin, polyester resin (C) and cross-linking agent (D) with specific ratio is had disclosed in patent documentation 3.But, when by this paint spraying in metal parts and plastic components, though no problem relative to the tack of plastic components, it is also difficult to say that compared with being coated with coating with aqueous, chipping resistance and light transmittance are abundant.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2012-213692 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2005-330339 publication
Patent documentation 3:WO2007/66827 publication
Summary of the invention
The problem that invention to solve
The present invention considers that above-mentioned aspect is made, and its object is to provide the method for forming layered coating film of a kind of film being formed and having the chipping resistance of excellence, tack, retouching, weatherability and ethanol petrol resistant relative to metal parts and plastic components.
Means needed for solution problem
nullThe present inventor has concentrated on studies to achieve these goals，Found that above-mentioned problem can be solved by a kind of method of forming layered coating film，Thus completing the present invention，It is used on coated article application aqueous successively the 1st pigmented finiss at this、In the method for forming layered coating film of 1 roasting mode of 3 applications of aqueous the 2nd pigmented finiss and clear dope，Use containing chlorine-free polyolefin-based resins (A)、Specific waterborne polyurethane resin (B)、There is the blocked polyisocyanate compound (C) of nonionic hydrophilic group and the coating of conductive pigment (D) as aqueous the 1st pigmented finiss (X)，It is characterized in that，This aqueous the 1st pigmented finiss (X) of application the cured coating film that thickness is 5 μm that makes it solidify and the obtain average transmittance at wavelength 360nm～420nm place is lower than 1%.
That is, the present invention provides following method of forming layered coating film.
Item 1.
A kind of method of forming layered coating film, it is the method for forming layered coating film being sequentially carried out following operation:
(1) on the coated article containing metal material and plastic material application aqueous the 1st pigmented finiss (X) and form the operation of the 1st uncured painted film；
(2) on the 1st uncured painted film obtained by operation (1) application aqueous the 2nd pigmented finiss (Y) and form the operation of the 2nd uncured painted film；
(3) on the 2nd uncured painted film obtained by operation (2) transparent paint coating (Z) and form the operation of uncured transparent coating；And
(4) operation by the 1st uncured painted film formed in operation (1)～(3), the 2nd uncured painted film and uncured transparent coating are heated and make this 3 films solidify simultaneously, it is characterized in that
Above-mentioned aqueous the 1st pigmented finiss (X) containing chlorine-free polyolefin-based resins (A), acid number be 1mgKOH/g～30mgKOH/g and at the temperature of 20 DEG C the waterborne polyurethane resin (B) that time is 5 minutes～20 minutes till film forming, the blocked polyisocyanate compound (C) with nonionic hydrophilic group and conductive pigment (D)
Application above-mentioned aqueous the 1st pigmented finiss (X) the cured coating film that thickness is 5 μm that makes it solidify and the obtain average transmittance at wavelength 360nm～420nm place is lower than 1%.
Invention effect
By the method for forming layered coating film of the present invention, even if not using priming paint no matter also can be formed relative to metal parts or the film being respectively provided with the chipping resistance of excellence, tack, retouching, weatherability and ethanol petrol resistant relative to plastic components.
Detailed description of the invention
Hereinafter, the method for forming layered coating film of the present invention is described in further detail.
In this manual, except there is situation about additionally expressing in this manual or except the situation of the clear and definite contradiction of context, singulative comprises single and multiple.
Operation (1)
In the operation (1) of the present invention, application aqueous the 1st pigmented finiss (X) on the coated article containing metal material and plastic material.Aqueous the 1st pigmented finiss (X) is coated on metal material and plastic material especially.As coated article, it does not have be particularly limited to, for instance can enumerate: automobile exterior panel portions such as passenger car, truck, motorcycle, buses；The auto parts such as bumper；The outside plate portion etc. of the home electric articles for use such as mobile phone, stereo set.
As metal parts, for instance can enumerate: the steel etc. of ferrum, aluminum, pyrite, copper, tinplate, rustless steel, galvanized steel and galvanized alloy (Zn-Al, Zn-Ni, Zn-Fe etc.).
Above-mentioned metal parts can also be the metal parts that its surface is implemented the surface treatments such as phosphate treated, chromate process and composite oxides process, and then can also be the metal parts being formed on primary coat film, this primary coat film utilizes bottom-coating to be formed.As bottom-coating, it is possible to enumerate such as electrocoating paint, wherein, it is preferable that cationic electrocoating paint.
Material as plastic components, such as it is particularly preferably a kind of the olefines making the carbon numbers 2～10 such as ethylene, propylene, butylene, hexene or polyolefin that two or more (being total to) is polymerized, in addition, it is also possible to enumerate: Merlon, ABS resin, urethane resin, polyamide etc..As these plastic components, for instance can enumerate: automobile exterior panel portions such as bumper, spoiler, grid, mud guards；The outside plate portion etc. of home electric articles for use.These plastic components can be suitable for carrying out ungrease treatment, washing process etc. by method known per se the aqueous of the application present invention the 1st pigmented finiss (X) is front.
Above-mentioned metal parts and plastic components can be assembled by known method.
Aqueous the 1st pigmented finiss (X)
As the aqueous the 1st pigmented finiss (X) of institute's application on the coated article containing above-mentioned metal material and plastic material, containing chlorine-free polyolefin-based resins (A), specific waterborne polyurethane resin (B), the blocked polyisocyanate compound (C) with non-aqueous hydrophilic group and conductive pigment (D).
It addition, the average transmittance that application aqueous the 1st pigmented finiss (X) the cured coating film that thickness is 5 μm that makes it solidify and obtain are at wavelength 360nm～420nm place is lower than 1%.
Chlorine-free polyolefin-based resins (A)
Chlorine-free polyolefin-based resins (A) for main framing with molecular polyolefin and imports the hydrophilic radical such as carboxyl in the molecule thereof and forms, it is usually preferred to unsaturated carboxylic acid or anhydride modified polyolefin (a).
Unsaturated carboxylic acid or anhydride modified polyolefin (a) generally can make unsaturated carboxylic acid or anhydride and polyolefin graft copolymerization obtain by method known per se.As can be used for the unsaturated carboxylic acid or the anhydride that modifiy, comprise aliphatic carboxylic acid or its acid anhydride that carbon number is 3～10, wherein, this aliphatic carboxylic acid or its acid anhydride contain at least 1, preferably 1 polymerism double bond and not chloride in 1 molecule, specifically, such as can enumerate: (methyl) acrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride etc., wherein, it is particularly preferred to maleic acid and maleic anhydride.Can change according to desired physical property of improved polyalkene etc. relative to the polyolefinic graft copolymerization amount utilizing this unsaturated carboxylic acid or its anhydride, but it is generally 0.5 weight %～4 weight % with polyolefinic solids by weight for benchmark, it is preferably 1 weight %～3 weight %, it is preferred that in the scope of 1.2 weight %～2.8 weight %.
On the other hand, 1 kind that makes the alkene that carbon number is 2～10 such as ethylene, propylene, butylene, hexene is such as comprised or the polyolefin not being chlorinated that two or more (being total to) is polymerized, it is particularly preferred to containing the propylene polyolefin as polymerized unit for modified polyolefin.The weight fraction of the propylene units in improved polyalkene considers from viewpoints such as the tacks with the intermiscibility and formation film of other composition, it is common that 0.5～1, it is particularly preferred to be 0.7～0.99, further particularly preferably in the scope of 0.8～0.99.
As said polyolefins, can be without using the polyolefin known per se not being chlorinated to restriction especially, but from the viewpoint of the polyolefinic narrow molecular weight distribution obtained and random copolymerization etc. also excellence, it is preferred to use single site catalysts is as polymerization catalyst the polyolefin by alkene (being total to) polymerization being manufactured.Single site catalysts is the polymerization catalyst of active site even structure (unit point), in this single site catalysts, it is particularly preferred to metallocene series catalysts.This metallocene series catalysts is by combining the metallocene (double; two (cyclopentadienyl group) metal complexs and derivant thereof) of the terres rares transistion metal compound as the IVB～group vib of the periodic table of elements or the transistion metal compound of VIII or IIIB race at least with a conjugation five-membered ring part, being prepared by the organo-aluminum compounds such as promoter and trimethyl aluminium such as the aikyiaiurnirsoxan beta of its activation or boron system.(being total to) polymerization of alkene can according to method known per se, such as by one side the alkene such as propylene or ethylene and hydrogen are supplied in reaction vessel on one side the method for continuous interpolation alkyl aluminum and Metallocene-type catalysts and carry out.
Above-mentioned unsaturated carboxylic acid or anhydride modified polyolefin (a) can also carry out acrylic acid modified further.Such as, as can be used for this acrylic acid modified acrylic acid series unsaturated monomer, it is possible to enumerate (methyl) acrylic acid C1～C20 Arrcostabs such as not chloride acrylic acid series unsaturated monomer, (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) stearyl acrylate base ester；(methyl) acrylic acid C1～C21 hydroxyalkyl acrylates such as (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 3-hydroxy propyl ester；(methyl) acrylic acid, (methyl) glycidyl acrylate, (methyl) acrylamide, (methyl) acrylonitrile etc. other acrylic monomer or enumerate styrene etc. further, these can individually use or combine use two or more.
It addition, in this manual, " (methyl) acrylic acid " refers to " acrylic or methacrylic acid ", and " (methyl) acrylate " refers to " acrylate or methacrylate ".
The acrylic acid modified of said polyolefins such as can pass through to operate as follows to carry out: first, make for the carboxyl in unsaturated carboxylic acid fabricated as described above or anhydride modified polyolefin, to there is the reaction such as reactive not chloride acrylic acid series unsaturated monomer, such as (methyl) glycidyl acrylate and import polymerism unsaturated group to polyolefin, then, making aforesaid propylene acid is that unsaturated monomer individually or combines two or more polyolefin (being total to) being imported with polymerism unsaturated group with this and is polymerized.Polyolefinic acrylic acid modified in the consumption that makes of aforesaid propylene acids unsaturated monomer can change according to desired physical property of improved polyalkene etc., but from the viewpoint of the tack etc. with the intermiscibility and formation film of other composition, generally it is preferably below 30 weight % with the solids by weight of the unsaturated carboxylic acid obtained or anhydride modified polyolefin (a) for benchmark, it is particularly preferably 0.1 weight %～20 weight %, further particularly preferably in the scope of 0.15 weight %～15 weight %.
Above-mentioned unsaturated carboxylic acid or anhydride modified polyolefin (a) can also be modified with the compound with polyoxyalkylene chain further.As the polyoxyalkylene chain in the compound with polyoxyalkylene chain, for instance can enumerate: the block chain etc. of polyoxyethylene chain, polyoxypropylene chains, polyoxyethylene and polyoxypropylene.
Number-average molecular weight in the above-mentioned generally preferable scope with 400～3,000, preferably 500～2,000 of compound with polyoxyalkylene chain.If this number-average molecular weight is less than 400, then cannot play the effect as hydrophilic group fully, it is possible to resistance to water is had undesirable effect, on the other hand, if this number-average molecular weight is more than 3,000, then at room temperature solidify and make dissolubility be deteriorated, it is possible to not easily operate.
From the viewpoint of with the intermiscibility of other composition, formed film and plastic components tack or with the interlayer tack etc. of topcoating film layer, expect that the fusing point of above-mentioned unsaturated carboxylic acid or anhydride modified polyolefin (a) is below 120 DEG C, it is preferably 60 DEG C～110 DEG C, it is preferred that in the scope of 70 DEG C～100 DEG C, and expect that its weight average molecular weight (Mw) is 10,000～230, in the scope of 000, preferably in 50, in the scope of 000～200,000, it is preferred that 60, in the scope of 000～150,000.
Additionally, from the viewpoint of formed film relative to the tack of plastic components or with the interlayer tack etc. of topcoating film layer, it is generally desirable to the melting caloric of above-mentioned unsaturated carboxylic acid or anhydride modified polyolefin (a) in the scope of 1mJ/mg～50mJ/mg, be especially desired in the scope of 2mJ/mg～50mJ/mg.
At this, the fusing point of above-mentioned unsaturated carboxylic acid or anhydride modified polyolefin (a) and melting caloric can be operated by obtaining: utilize Differential Scanning Calorimetry measurement apparatus " DSC-5200 " (manufacture of Seiko Electronics Industry Company, trade name), use improved polyalkene 20mg to be warming up to 150 DEG C with programming rate 10 DEG C/min from-100 DEG C and measure heat.The adjustment of the fusing point of above-mentioned unsaturated carboxylic acid or anhydride modified polyolefin (a) can by change polyolefinic monomer composition, particularly the amount of 'alpha '-olefin monomers carry out.It addition, when melting caloric is not easily obtained, can passing through temporarily to heat to 120 DEG C measuring samples, after being then cooled to room temperature with 10 DEG C/min, standing more than 2 days, thus measuring heat.
Additionally, the weight average molecular weight of above-mentioned unsaturated carboxylic acid or anhydride modified polyolefin (a) is the value weight average molecular weight utilizing gel permeation chromatography to record obtained with the weight average molecular weight of polystyrene for basis conversion, as gel permeation chromatography, use " HLC/GPC150C " (manufacture of Waters company, 60cm × 1) and the o-dichlorohenzene as solvent, with column temperature 135 DEG C, flow 1.0ml/min measurement.Inject sample by preparing dissolving 1～3 hour at 140 DEG C relative to the o-dichlorohenzene 3.4ml mode being the solution concentration of polyolefin 5mg.It addition, as the post for gel permeation chromatography, it is possible to use " GMHHR-H (S) HT " (manufacture of east Cao's (strain) company, trade name).
And then, above-mentioned unsaturated carboxylic acid or anhydride modified polyolefin (a) are from the viewpoint of the tack etc. with the intermiscibility or formation film of other composition, it is generally desirable to the ratio (Mw/Mn) of weight average molecular weight and number-average molecular weight in the scope of 1.5～7.0, preferably in the scope of 1.8～6.0, it is preferred that in the scope of 2.0～4.0.
Above-mentioned chlorine-free polyolefin-based resins (A) can, by disperseing to carry out moisture dispersion in an aqueous medium by unsaturated carboxylic acid described above or anhydride modified polyolefin (a), generally can be passed through part or all of the carboxyl in unsaturated carboxylic acid or anhydride modified polyolefin (a) to be neutralized with amines and/or utilize emulsifying agent to carry out moisture to dissipate.From the viewpoint of improving water dispersible, it is desirable to use the moisture dispersion by neutralizing and emulsifying agent carries out simultaneously.
As the amines for neutralizing, for instance can enumerate: the tertiary amines such as triethylamine, tri-n-butylamine, dimethylethanolamine, triethanolamine；The secondary amine such as diethylamine, dibutyl amine, diethanolamine, morpholine；The primary amine such as propylamine, ethanolamine etc..Its when using these amines makes consumption preferably with respect to the carboxyl in unsaturated carboxylic acid or anhydride modified polyolefin (a) generally in the scope of 0.1 molar equivalent～1.0 molar equivalent.
nullAs mentioned emulsifier，Such as can enumerate，Polyoxyethylene list oleyl ether、Polyoxyethylene list octadecyl ether、Polyoxyethylene list lauryl ether、Polyoxyethylene tridecyl ether、Polyoxyethylene phenyl ether、Ethylene nonyl phenyl ether、NONIN HS 240、Vinlub 73、Polyoxyethylene monostearate、Polyoxyethylene monooleate、Sorbitan mono-laurate、Sorbitan monostearate、Sorbitan trioleate、The nonionic class emulsifying agents such as polyoxyethylene 20 sorbitan monolaurate，Alkyl sulfonic acid、Alkyl benzene sulphonate、The anionic species emulsifying agents etc. such as the sodium salt of alkyl phosphoric acid etc. or ammonium salt，And then，Can also use and 1 molecule has the polyoxyalkylenes such as anionic property group and polyoxyethylene groups or polyoxypropylene base、Anionic emulsifier containing polyoxyalkylenes or 1 molecule have the reactive anionic emulsifier etc. of this anionic property group and polymerism unsaturated group.These emulsifying agents can individually use or combine and use two or more.
Relative to solid constituent 100 weight portion of above-mentioned unsaturated carboxylic acid or anhydride modified polyolefin (a), above-mentioned emulsifying agent generally can use in the scope of 1 mass parts～20 weight portion.
The emulsification method of above-mentioned unsaturated carboxylic acid or anhydride modified polyolefin (a) is not particularly limited, it is possible to adopt the known methods such as such as Phase inversion emulsification, D phase emulsifying, forced emulsification, gel emulsifying, self emulsifying, reversion emulsifying, high-pressure emulsification.Wherein, from the viewpoint of the outward appearance of the film obtained and resistance to water, it is preferable that the method utilizing self emulsifying.
Make and contain the chlorine-free polyolefin-based resins (A) through acrylic acid modified unsaturated carboxylic acid or anhydride modified polyolefin further it addition, the aqueous dispersion of the unsaturated carboxylic acid as above obtained or anhydride modified polyolefin (a) can also be deposited by the unsaturated carboxylic acid being water dispersible or anhydride modified polyolefin (a) by the acrylic acid series listed in acrylic acid modified explanation unsaturated monomer is carried out emulsion polymerization in case.
From the viewpoint of the chipping resistance of the film obtained, tack, retouching, weatherability and ethanol petrol resistant, with the total resin solid content quality in aqueous the 1st pigmented finiss (X) for benchmark, the content of above-mentioned chlorine-free polyolefin-based resins (A) is 10 mass %～60 mass %, it is preferably 20 mass %～50 mass %, more preferably 25 mass %～50 mass %.
Waterborne polyurethane resin (B)
Waterborne polyurethane resin (B) refers to can using water as scattered polyurethane resin in the aqueous medium of primary solvent or disperse medium, as the form in aqueous medium, can be any one of water solublity type, colloidal dispersion type, emulsion types and slurry types, but be preferably colloidal dispersion type or emulsion types.
As above-mentioned waterborne polyurethane resin (B), waterborne polyurethane resin known per se can be used, the waterborne polyurethane resin obtained preferably for example by following operation, namely, when there is the glycol as chain elongation agent, when 1 molecule such as diamidogen at least has the low molecular weight compound of 2 reactive hydrogens, polyurethane is optionally carried out further the material that chain elongation is obtained, it can stably disperse in an aqueous medium or dissolve and use, this polyurethane is by making PEPA, polycarbonate polyol, the polyhydric alcohol such as polyether polyol or low-molecular-weight hydroxy-containing compounds react obtained with polyisocyanate.
As above-mentioned polyol component, from the viewpoint of the chipping resistance of the film obtained, tack, retouching, weatherability and ethanol petrol resistant, it is particularly preferred to PEPA and polyether polyol.
The above-mentioned PEPA used in manufacture as above-mentioned waterborne polyurethane resin (B), such as can enumerate: by making 1, the aliphatic diols such as 4-butanediol, 1,6-hexanediol and the aliphatic dicarboxylic acid such as adipic acid, decanedioic acid react obtained PEPA；By making this aromatic dicarboxylic acid such as aliphatic diol and p-phthalic acid obtained PEPA etc. of reaction, as polycarbonate polyol, such as can enumerate: by making 1,6-hexanediol, 3-methyl isophthalic acid, the glycol such as 5-pentanediol and the carbonates such as dimethyl carbonate react obtained polycarbonate polyol etc., as polyether polyol, for instance can enumerate: by making the obtained poly alkylene glycol etc. of the ring-opening polymerisations such as the oxirane of Polyethylene Glycol, polypropylene glycol and polytetramethylene glycol etc., expoxy propane.Additionally, as above-mentioned polyisocyanate, for instance can enumerate: the aliphatic such as hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate and alicyclic diisocyanate and their isocyanurate ring addition product etc..As above-mentioned polisocyanate component, from the viewpoint of the chipping resistance of the film obtained, tack, retouching, weatherability and ethanol petrol resistant, it is particularly preferred that isophorone diisocyanate.
And, for the glycol as chain elongation agent, for instance can enumerate: ethylene glycol, BDO, 1,5-PD, 3-methyl isophthalic acid, 5-pentanediol, cyclohexanediol etc., as diamidogen, for instance can enumerate: ethylenediamine, propane diamine, xylylene diamine etc..
As making above-mentioned waterborne polyurethane resin (B) method of stably dispersion or dissolving in water, for instance following method can be used.
(1) by using the carboxylic glycol such as dihydromethyl propionic acid, dimethylolpropionic acid to introduce carboxyl as the manufacture raw material of polyurethane to polyurethane, to give hydrophilic to polyurethane by part or all neutralizing this carboxyl, be dispersed or dissolved in water by self emulsifying.
(2) as the polyhydric alcohol manufacturing raw material of polyurethane, use hydrophilic polyol as Polyethylene Glycol, manufacture water-soluble polyurethane, be dispersed or dissolved in water.
(3) end-capping reagents such as oxime, alcohol, phenol, mercaptan, amine, sodium sulfite are used to terminate to reacting complete polyurethane or terminal isocyanate group, by the polyurethane nonionic obtained and/or cationic emulsifier and mechanical shear stress Forced Dispersion in water.
(4) urethane prepolymer with terminal isocyanate group is mixed with water/emulsifying agent/chain elongation agent, carry out dispersion with mechanical shear stress simultaneously and quantify with macromolecule.
As above-mentioned waterborne polyurethane resin (B), it is not limited to the polyurethane obtained by single manufacture method, it is possible to use by the mixture of the polyurethane that various methods obtain.
From the viewpoint of the chipping resistance of the film obtained, tack, retouching, weatherability and ethanol petrol resistant, the acid number of waterborne polyurethane resin (B) is in the scope of 1mgKOH/g～30mgKOH/g, preferably in the scope of 3mgKOH/g～25mgKOH/g, it is preferred that in the scope of 5mgKOH/g～20mgKOH/g.
The aspect of the chipping resistance of the film obtained, tack, retouching, weatherability and ethanol petrol resistant considers, above-mentioned waterborne polyurethane resin (B) time till film forming at the temperature of 20 DEG C is 5 minutes～20 minutes, it is preferably 10 minutes～20 minutes, more preferably 12 minutes～18 minutes.
At this, the so-called time till film forming refers to that waterborne polyurethane resin forms the time needed for continuous film.The waterborne polyurethane resin time to film forming measures as follows.
Using the waterborne polyurethane resin solution coating that solid constituent is adjusted to 28% by metering bar coater to make wet-film thickness on a pet film under room temperature 20 DEG C, humidity 60% atmosphere is 40 μm.The starting point of measure of time will be set to after firm application, on film, the height of 1cm uses dropper dropping 0.3mL ion exchange water at regular intervals, the change of the drop diameter just dripped in latter 1 second is set to terminal when below 1mm, the time of origin-to-destination is set to " waterborne polyurethane resin time till film forming ".
From the viewpoint of the chipping resistance of the film obtained, tack, retouching, weatherability and ethanol petrol resistant, preferably, mean diameter in above-mentioned waterborne polyurethane resin (B) aqueous medium is 70nm～250nm, it is preferably 80nm～230nm, more preferably 100nm～200nm.
In this manual, mean diameter is the value using dynamic light scattering method particle size distribution measurement apparatus to record at 20 DEG C after using deionized water dilution by conventional method.As this dynamic light scattering method particle size distribution measurement apparatus, for instance " sub-micron grade particle analyzer N5 " (trade name, BeckmanCoulter company manufactures) can be used.
From the viewpoint of the chipping resistance of the film obtained, tack, retouching, weatherability and ethanol petrol resistant, with the resin solid content quality total amount in aqueous the 1st pigmented finiss (X) for benchmark, preferably, the content of the above-mentioned waterborne polyurethane resin (B) in aqueous the 1st pigmented finiss (X) is suitably for 10 mass %～50 mass %, it is preferably 10 mass %～40 mass %, more preferably 15 mass %～30 mass %.
There is the blocked polyisocyanate compound (C) of nonionic hydrophilic group
Have that a part of NCO that the blocked polyisocyanate compound (C) of nonionic hydrophilic group is the polyisocyanate compounds in 1 molecule with more than 2 NCOs is modified by nonionic hydrophilic group, remaining some or all of NCO is blocked the compound of agent end-blocking.
The blocked polyisocyanate compound (C) with nonionic hydrophilic group can be obtained by known method.Such as can obtain having by making the active hydrogen-contg compound (c2) with nonionic hydrophilic group and end-capping reagent (c3) and the NCO in the polyisocyanate compounds (c1) in 1 molecule with more than 2 NCOs react the blocked polyisocyanate compound (following, the blocked polyisocyanate compound with nonionic hydrophilic group as above obtained is called " (C1) ") of nonionic hydrophilic group.
When the NCO in making above-mentioned polyisocyanate compounds (c1) and the above-mentioned active hydrogen-contg compound (c2) with nonionic hydrophilic group and end-capping reagent (c3) react, this polyisocyanate compounds (c1), the active hydrogen-contg compound (c2) and end-capping reagent (c3) with hydrophilic group reaction sequence be not particularly limited.Specifically, can enumerate: after a part for the active hydrogen-contg compound (c2) and the NCO in polyisocyanate compounds (c1) that make to have hydrophilic group is reacted, the method that remaining NCO end-capping reagent (c3) is terminated；After a part for NCO in polyisocyanate compounds (c1) being terminated with end-capping reagent (c3), make the method that the active hydrogen-contg compound (c2) with hydrophilic group reacts with remaining NCO；And make the method etc. that the active hydrogen-contg compound (c2) with hydrophilic group and end-capping reagent (c3) react simultaneously with the NCO in polyisocyanate compounds (c1).
Polyisocyanate compounds (c1)
Polyisocyanate compounds (c1) is the compound at least in 1 molecule with 2 NCOs, for instance can enumerate: aliphatic polymeric isocyanate, alicyclic polymeric isocyanate, aromatic-aliphatic polyisocyanate, aromatic poly-isocyanate, this polyisocyanate derivant etc..
As above-mentioned aliphatic polymeric isocyanate, such as can enumerate: trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-trimethylene diisocyanate, 1,2-tetramethylene diisocyanate, 2,3-tetramethylene diisocyanate, 1,3-tetramethylene diisocyanate, 2,4,4-or 2,2, the aliphatic diisocyanates such as 4-trimethyl hexamethylene diisocyanate, dimer acid diisocyanate, 2,6-bis-isocyanato-methyl caproates (trivial name: lysinediisocyanate)；2,6-bis-isocyanato-caproic acid 2-isocyanato ethyl, 1,6-bis-isocyanato--3-isocyanatomethyl hexane, 1,4,8-tri-isocyanato-octane, 1,6,11-tri-isocyanato-hendecane, 1,8-bis-isocyanato--4-two isocyanatomethyl octane, 1,3,6-tri-isocyanato-hexane, 2,5, the aliphatic triisocyanates etc. such as 7-trimethyl-1,8-two isocyanato--5-isocyanatomethyl octane.
As above-mentioned alicyclic polymeric isocyanate, such as can enumerate: 1, 3-cyclopentene diisocyanate, 1, 4-cyclohexane diisocyanate, 1, 3-cyclohexane diisocyanate, 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexylisocyanate (trivial name: isophorone diisocyanate), 4-methyl isophthalic acid, 3-cyclohexene diisocyanate (trivial name: hydrogenation TDI), 2-methyl isophthalic acid, 3-cyclohexene diisocyanate, 1, 3-or 1, double, two (isocyanatomethyl) hexamethylene (trivial name: hydrogenated xylene diisocyanate) of 4-or its mixture, di-2-ethylhexylphosphine oxide (4, 1-hexamethylene two base) diisocyanate (trivial name: hydrogenation MDI), the alicyclic diisocyanates such as norbornene alkyl diisocyanate；null1,3,5-tri-isocyanatocyclohexane、1,3,5-trimethyl isocyanatocyclohexane、2-(3-isocyanatopropyl)-2,5-bis-(isocyanatomethyl)-dicyclo (2.2.1) heptane、2-(3-isocyanatopropyl)-2,6-bis-(isocyanatomethyl)-dicyclo (2.2.1) heptane、3-(3-isocyanatopropyl)-2,5-bis-(isocyanatomethyl)-dicyclo (2.2.1) heptane、5-(2-isocyanatoethyl)-2-isocyanatomethyl-3-(3-isocyanatopropyl)-dicyclo (2.2.1) heptane、6-(2-isocyanatoethyl)-2-isocyanatomethyl-3-(3-isocyanatopropyl)-dicyclo (2.2.1) heptane、5-(2-isocyanatoethyl)-2-isocyanatomethyl-2-(3-isocyanatopropyl)-dicyclo (2.2.1)-heptane、The alicyclic triisocyanates etc. such as 6-(2-isocyanatoethyl)-2-isocyanatomethyl-2-(3-isocyanatopropyl)-dicyclo (2.2.1) heptane.
As above-mentioned aromatic-aliphatic polyisocyanate, such as can enumerate: di-2-ethylhexylphosphine oxide (4,1-phenylene) diisocyanate (trivial name: MDI), 1,3-or 1,4-XDI or its mixture, ω, ω '-two isocyanato--1,4-diethylbenzene, 1,3-or Isosorbide-5-Nitrae-bis-(1-isocyanato--1-Methylethyl) araliphatic diisocyanate such as benzene (trivial name: tetramethylxylene diisocyanate) or its mixture；The aromatic-aliphatic triisocyanates etc. such as 1,3,5-tri-isocyanatomethylbenzene.
As above-mentioned aromatic poly-isocyanate, such as can enumerate: metaphenylene diisocyanate, to phenylene vulcabond, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4 toluene diisocyanate (trivial name: 2,4-TDI) or 2,6-toluene di-isocyanate(TDI) (trivial name: 2,6-TDI) or the aromatic diisocyanate such as its mixture, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate；Triphenyl methane-4,4', 4 " aromatic tri-isocyanates such as-triisocyanate, 1,3,5-tri-isocyanato-benzene, 2,4,6-tri-isocyanato-toluene；The aromatic series tetraisocyanates etc. such as 4,4'-diphenyl methane-2,2', 5,5'-tetraisocyanate.
Additionally, derivant as above-mentioned polyisocyanate, for instance can enumerate: the dimer of above-mentioned polyisocyanate, trimer, biuret, allophanate, urea diketone, urea imines, isocyanuric acid ester, diazine triketone, polymethylene polyphenyl base polyisocyanate (thick MDI, polymeric MDI), thick TDI etc..
As above-mentioned polyisocyanate and derivant thereof, can individually use or can also be used two or more simultaneously.Additionally, in these polyisocyanate, as above-mentioned polyisocyanate compounds (c1), it is not likely to produce flavescence when heating, it is preferable that aliphatic diisocyanate, alicyclic diisocyanate and their derivant from the viewpoint of the blocked polyisocyanate compound (C1) with nonionic hydrophilic group obtained.Wherein, from the viewpoint of the flexibility of the film formed improves, it is preferred that aliphatic diisocyanate and derivant thereof.
It addition, as above-mentioned polyisocyanate compounds (c1), it is possible to use make the prepolymer that above-mentioned polyisocyanate and derivant thereof are reacted when NCO is excessive with the compound that can react with this polyisocyanate.As the compound that can react with this polyisocyanate, for instance can enumerate: there is the compound of hydroxyl, amino isoreactivity hydrogen, specifically, for instance polyhydric alcohol, low molecular weight polyester resin, amine, water etc. can be used.
Additionally, as above-mentioned polyisocyanate compounds (c1), it is possible to use the polymer of the polymerism unsaturated monomer containing NCO, maybe should polymerism unsaturated monomer containing NCO with should the copolymer of polymerism unsaturated monomer beyond the polymerism unsaturated monomer containing NCO.
From the viewpoint of the intermiscibility of the reactivity of the blocked polyisocyanate compound (C1) with nonionic hydrophilic group obtained and the compositions containing this blocked polyisocyanate compound and other paint ingredient, several mean molecule quantities of above-mentioned polyisocyanate compounds (c1) are preferably in 300～20, in the scope of 000, more preferably in 400～8, in the scope of 000, it is preferred that 500～2, in the scope of 000.
Additionally, from the viewpoint of the intermiscibility of the reactivity of the blocked polyisocyanate compound (C1) with nonionic hydrophilic group obtained and this blocked polyisocyanate compound (C1) with nonionic hydrophilic group and other paint ingredient, the average isocyanate ester functional group number in above-mentioned polyisocyanate compounds (c1) preferably 1 molecule is in the scope of 2～100.As lower limit, consider from the reactive viewpoint improving the blocked polyisocyanate compound (C1) with nonionic hydrophilic group obtained, more preferably 3.As the upper limit, from the viewpoint of prevent gelation when manufacturing blocked polyisocyanate compound (C1) with nonionic hydrophilic group, more preferably 20.
There is the active hydrogen-contg compound (c2) of nonionic hydrophilic group
As the active hydrogen-contg compound with nonionic hydrophilic group, for instance the active hydrogen-contg compound of polyoxyalkylenes can be preferably used.As above-mentioned polyoxyalkylenes, for instance can enumerate: polyoxyethylene groups, polyoxypropylene base, polyoxyethylene (oxypropylene) base etc., these can be used alone or combine and use two or more.Wherein, from the viewpoint of the storage stability of the blocked polyisocyanate compound (C1) with nonionic hydrophilic group obtained, it is preferable that have the active hydrogen-contg compound of polyoxyethylene groups.
Considering from viewpoints such as the storage stability of the blocked polyisocyanate compound (C1) with nonionic hydrophilic group obtained and the resistances to water of film that formed, the above-mentioned active hydrogen-contg compound with polyoxyethylene groups preferably has more than 3 continuous print oxyethylene groups, preferably has 5～100 continuous print oxyethylene groups, more preferably has 8～45 continuous print oxyethylene groups.
It addition, the above-mentioned active hydrogen-contg compound with polyoxyethylene groups is except continuous print oxyethylene group, it is also possible to containing the oxyalkylene group beyond oxyethylene group.As the oxyalkylene group beyond this oxyethylene group, for instance can enumerate: oxypropylene group, oxygen cyclobutenyl, oxygen hexenyl etc..From the viewpoint of obtain containing blocked polyisocyanate compound compositions moisture dissipate after storage stability, in the molar ratio of the oxyethylene group in oxyalkylene in the above-mentioned active hydrogen-contg compound with the polyoxyethylene groups scope preferably in 20～100 moles of %, in the scope more preferably in 50～100 moles of %.If the molar ratio of the oxyethylene group in oxyalkylene group is lower than 20 moles of %, then cannot fully giving hydrophilic, the storage stability of the blocked polyisocyanate compound (C1) with nonionic hydrophilic group obtained reduces sometimes.
Additionally, from the viewpoint of the storage stability of the blocked polyisocyanate compound (C1) with nonionic hydrophilic group obtained and the resistance to water of film that formed, the number-average molecular weight of the above-mentioned active hydrogen-contg compound with nonionic hydrophilic group is preferably in 200～2, in the scope of 000.As the lower limit of number-average molecular weight, from the viewpoint of the storage stability of the blocked polyisocyanate compound (C1) with nonionic hydrophilic group obtained, more preferably 300, more preferably 400.As the upper limit, from the viewpoint of the resistance to water of the film formed by the aqueous the 1st pigmented finiss (X) of the present invention, more preferably 1,500, more preferably 1,200.
nullAs the above-mentioned active hydrogen-contg compound with nonionic hydrophilic group，Such as can enumerate: the polyalkylene glycol monoalkyl ethers such as poly glycol monomethyl ether and polyethyleneglycol ether (another name: ω-alkoxy polyoxy)、The polypropylene glycol monoalky lethers such as polypropylene glycol monomethyl ether and polypropylene glycol list ether (another name: ω-alkoxyl polyoxypropylene)、ω-methoxy polyoxyethylene (oxypropylene)、ω-the alkoxy polyoxy (oxypropylene) such as ω-ethyoxyl polyoxyethylene (oxypropylene)、Polyethylene Glycol (propylene glycol) monomethyl ether、Polyethylene Glycol (propylene glycol) monoalky lethers such as the single ether of Polyethylene Glycol (propylene glycol)、Polyethylene Glycol、Polypropylene glycol、Polyethylene Glycol (propylene glycol)、α-(aminoalkyl)-ω-alkoxy polyoxy、α-(aminoalkyl)-ω-alkoxyl polyoxypropylene、α-(aminoalkyl)-ω-alkoxy polyoxy (oxypropylene) etc.，These can be used alone or combine and use two or more.Wherein, it is preferable that poly glycol monomethyl ether, polyethyleneglycol ether and Polyethylene Glycol, more preferably poly glycol monomethyl ether.
It addition, in this manual, " Polyethylene Glycol (propylene glycol) " refers to the copolymer of ethylene glycol and propylene glycol, comprises any one in block copolymer and random copolymer.
It addition, as the market sale product of above-mentioned poly glycol monomethyl ether, for instance can enumerate: " UNIOXM-400 ", " UNIOXM-550 ", " UNIOXM-1000 " of Japan Oil Co's manufacture, " UNIOXM-2000 " etc..Additionally, market sale product as above-mentioned Polyethylene Glycol, for instance can enumerate: " PEG#200 ", " PEG#300 ", " PEG#400 " of Japan Oil Co's manufacture, " PEG#600 ", " PEG#1000 ", " PEG#1500 ", " PEG#1540 ", " PEG#2000 " etc..
From the storage stability of the blocked polyisocyanate compound (C1) with nonionic hydrophilic group obtained and curable and the tack of film that formed by the aqueous the 1st pigmented finiss (X) of the present invention, flatness, the viewpoint of distinctiveness and resistance to water considers, when a part of NCO in making polyisocyanate compounds (c1) reacts with the above-mentioned active hydrogen-contg compound (c2) with nonionic hydrophilic group, reaction ratio for isocyanate compound (c1) with the active hydrogen-contg compound (c2) with nonionic hydrophilic group, with 1 mole isocyanate base in polyisocyanate compounds (c1) be the reactive hydrogen in the preferred active hydrogen-contg compound of benchmark molal quantity in the scope of 0.03 mole～0.6 mole.As the upper limit, from the viewpoint of the curable of the blocked polyisocyanate compound (C1) with nonionic hydrophilic group obtained and the resistance to water of film that formed by the aqueous the 1st pigmented finiss (X) of the present invention, it is more preferably 0.4, more preferably 0.3.As lower limit, from the viewpoint of the storage stability of the blocked polyisocyanate compound (C1) with nonionic hydrophilic group obtained and the tack of film, flatness, distinctiveness and the resistance to water that are formed by the aqueous the 1st pigmented finiss (X) of the present invention, it is more preferably 0.04, more preferably 0.05.
End-capping reagent (c3)
As end-capping reagent, such as can enumerate: phenol system, alcohol system, active methylene group system, mercaptan system, acid amide system, acid imide system, imidazoles system, Urea Series, oxime system, carbamic acid system, amine system, imines system etc., these can be used alone or use two or more simultaneously.End-capping reagent is as follows more specifically.
(1) phenol system；Phenol, cresol, ethyl-phenol, butylphenol etc.,
(2) alcohol system；Ethylene glycol, benzyl alcohol, methanol, ethanol etc.,
(3) active methylene group system；Diester malonate, acetoacetic ester, isobutyryl acetas etc.,
(4) mercaptan system；Butyl mercaptan, lauryl mercaptan etc.,
(5) acid amide system；Acetanilide, amide, epsilon-caprolactams, δ-valerolactam, butyrolactam etc.,
(6) acid imide system；Butanimide, maleimide etc.,
(7) imidazoles system；Imidazoles, 2-methylimidazole etc.,
(8) Urea Series；Carbamide, thiourea, ethylidene-urea etc.,
(9) oxime system；Formaldoxime, aldoxime, methyl ethyl ketone oxime, cyclohexyl ketoxime etc.,
(10) carbamic acid system；N-phenylcarbamic acid phenyl ester etc.,
(11) amine system；Diphenylamine, aniline, carbazole etc.,
(12) imines system；Aziridine, polymine etc..
The end-blockingization reaction utilizing the NCO of end-capping reagent (c3) optionally uses catalysts.As this catalysts, for instance can enumerate: alkali compoundss such as metal hydroxides, metal alkoxide, metal carboxylate, metal acetyl acetate, the hydroxide of salt, carboxylate, the slaine of activity methene compound, the salt of activity methene compound, amino silicone alkanes, amine, phosphine classes.Wherein, as salt, it is preferable that ammonium salt, salt, sulfonium salt.Generally, with the total solid constituent quality of polyisocyanate compounds (c1) and end-capping reagent (c3) for benchmark, this catalysts make consumption preferably in 10ppm～10, in the scope of 000ppm, it is preferred that in 20ppm～5, in the scope of 000ppm.
It addition, utilize the end-blocking reaction of the NCO of above-mentioned end-capping reagent (c3) can carry out at 0 DEG C～150 DEG C, it is possible to use solvent.In this case, as solvent, it is preferable that non-protonic solvent, it is particularly preferred to ester, ether, N-alkylamide, ketone etc..If reaction carry out according to target, then can by add acid composition the alkali compounds as catalyst is neutralized, make reaction stop.
In utilizing the reaction of the end-blockingization of NCO of end-capping reagent (c3), the consumption that makes of end-capping reagent (c3) is not particularly limited, 0.1 mole～3 moles are used, it is preferred to use 0.2 mole～2 moles preferably with respect to 1 mole isocyanate base in polyisocyanate compounds (c1).It addition, the end-capping reagent not reacted with the NCO in polyisocyanate compounds (c1) can remove after end-blockingization reaction terminates.
Wherein, from the viewpoint of the curability at low temperatures of the film formed by the aqueous the 1st pigmented finiss (X) of the present invention, end-capping reagent (c3) is preferably active methylene group system.
From the viewpoint of the stability of the aqueous the 1st pigmented finiss (X) of the present invention, particularly preferred form as the blocked polyisocyanate compound (C1) with nonionic hydrophilic group, it is possible to enumerate: what have the blocked isocyanate base shown in following formula (IV) has nonionic hydrophilic group blocked polyisocyanate compound (C1-1) and have the blocked isocyanate base shown in following logical formula V and have the blocked polyisocyanate compound (C1-2) of nonionic hydrophilic group.
[chemical formula 1]
[in formula (IV), R1Represent the alkyl of carbon number 1～12 independently, it is possible to identical, it is also possible to different.]
[chemical formula 2]
[in formula (V), R6And R7Represent the alkyl of carbon number 1～12 independently.]
There is the blocked polyisocyanate compound (C1-1) of nonionic hydrophilic group
The blocked polyisocyanate compound (C1-1) with nonionic hydrophilic group is the blocked polyisocyanate compound with the blocked isocyanate base shown in above-mentioned formula (IV).
Wherein, as the above-mentioned end-capping reagent (c3) of one of the raw material of this blocked polyisocyanate compound, from the viewpoint of the end-capping reagent compound that can use the active methylene group class that can manufacture relatively easily, R1It is preferably the alkyl of carbon number 1～3.Wherein, from the viewpoint of improve obtain there is the blocked polyisocyanate compound (C1) of nonionic hydrophilic group and the intermiscibility of other paint ingredient, R1It is preferably the alkyl of carbon number 2 or 3, from the viewpoint of the storage stability of the blocked polyisocyanate compound (C1) with nonionic hydrophilic group obtained and the flatness of film formed by the aqueous the 1st pigmented finiss (X) of the present invention and distinctiveness, R1More preferably isopropyl.
The above-mentioned blocked polyisocyanate compound (C1-1) with nonionic hydrophilic group such as can obtain by making the dialkyl malonate of above-mentioned polyisocyanate compounds (c1) and the active hydrogen-contg compound (c2) and the alkyl with carbon number 1～12 as end-capping reagent (c3) with nonionic hydrophilic group react.
As above-mentioned dialkyl malonate, such as can enumerating: dimethyl malenate, diethyl malonate, malonic acid di-n-propyl ester, Diisopropyl malonate, malonic acid di-n-butyl, malonic acid diisobutyl ester, malonic acid di-secondary butyl ester, malonic acid di tert butyl carbonate, malonic acid two n-pentyl ester, the just own ester of malonic acid two, malonic acid two (2-ethylhexyl) ester etc., these can be used alone or combine and use two or more.Wherein, preferred dimethyl malenate, diethyl malonate, malonic acid di-n-propyl ester, Diisopropyl malonate, malonic acid di-n-butyl, malonic acid diisobutyl ester, malonic acid di-secondary butyl ester, malonic acid di tert butyl carbonate, more preferably diethyl malonate, malonic acid di-n-propyl ester, Diisopropyl malonate, it is preferred that Diisopropyl malonate.
There is the blocked polyisocyanate compound (C1-2) of nonionic hydrophilic group
The blocked polyisocyanate compound (C1-2) with nonionic hydrophilic group is the blocked polyisocyanate compound with the blocked isocyanate base shown in above-mentioned logical formula V.
Wherein, as the above-mentioned end-capping reagent (c3) of one of the raw material of this blocked polyisocyanate compound, from the viewpoint of the end-capping reagent compound that can use the active methylene group class that can manufacture relatively easily, R6And R7It is preferably the alkyl of carbon number 1～3.Wherein, from the viewpoint of improve obtain there is the blocked polyisocyanate compound (C1) of nonionic hydrophilic group and the intermiscibility of other paint ingredient, R6 and R7 is preferably the alkyl of carbon number 2 or 3, from the viewpoint of the storage stability of the blocked polyisocyanate compound (C1) with nonionic hydrophilic group obtained, the aqueous the 1st pigmented finiss (X) of the present invention flatness of film formed and distinctiveness, R6And R7More preferably isopropyl.
The above-mentioned blocked polyisocyanate compound (C1-2) with nonionic hydrophilic group such as by making above-mentioned polyisocyanate compounds (c1) and can have the active hydrogen-contg compound (c2) of nonionic hydrophilic group and reacts with the isobutyryl acetas as end-capping reagent (c3), the alkyl with carbon number 1～12 acetoacetic ester or the alkyl with carbon number 1～12 and obtain.Wherein, as end-capping reagent (c3), it is preferred to use there is the isobutyryl acetas of the alkyl of carbon number 1～12 and react and obtain.
As above-mentioned isobutyryl acetas; such as can enumerating: isobutyryl methyl acetate, ethyl isobutyryl acetate, isobutyryl n-propyl acetate, isobutyryl isopropyl acetate, isobutyryl n-butyl acetate, isobutyryl isobutyl acetate, isobutyryl sec-butyl acetate, isobutyryl tert-butyl acetate, isobutyryl n-amyl acetate, isobutyryl n-hexyl acetate, isobutyryl acetic acid 2-Octyl Nitrite, isobutyryl phenylacetate, isobutyryl benzyl acetate etc., these can be used alone or combine and use two or more.Wherein, it is preferable that isobutyryl methyl acetate, ethyl isobutyryl acetate and isobutyryl isopropyl acetate.
As above-mentioned acetoacetic ester, such as can enumerating: methyl acetoacetate, ethyl acetoacetate, acetoacetic acid n-propyl, isopropyl acetoacetate, the positive butyl ester of acetoacetic acid, isobutyl acetoacetate, acetoacetic acid second butyl ester, tert-butyl acetoacetate, acetoacetic acid n-pentyl ester, the just own ester of acetoacetic acid, acetoacetic acid 2-Octyl Nitrite, acetoacetic acid phenyl ester, acetoacetic acid benzene methyl etc., these can be used alone or combine and use two or more.Wherein, it is preferable that methyl acetoacetate, ethyl acetoacetate and isopropyl acetoacetate.
In the present invention, particularly consider in the stability water, as the blocked polyisocyanate compound (C) with nonionic hydrophilic group, further secondary alcohol (c4) and the above-mentioned blocked polyisocyanate compound (C1) with nonionic hydrophilic group the is reacted obtained blocked polyisocyanate compound (following, the blocked polyisocyanate compound with nonionic hydrophilic group that as above obtain is called " (C2) ") with nonionic hydrophilic group is preferably used.
There is the blocked polyisocyanate compound (C2) of nonionic hydrophilic group
There is the blocked polyisocyanate compound (C2) of nonionic hydrophilic group such as to pass through to make the above-mentioned blocked polyisocyanate compound (C1) with nonionic hydrophilic group react with the secondary alcohol (c4) shown in following formula (VI) and obtain.
[chemical formula 3]
[in formula (VI), R2、R4And R5Represent the alkyl of carbon number 1～12, R independently3Represent the straight-chain of carbon number 1～12 or the alkylidene of branched.]
Secondary alcohol (c4)
Secondary alcohol (c4) is the compound shown in above-mentioned formula (VI).Wherein, consider from the reactive viewpoint improving the above-mentioned blocked polyisocyanate compound (C1) and above-mentioned secondary alcohol (c4) with nonionic hydrophilic group, R2It is preferably methyl.If it addition, R3、R4And R5Respective carbon number is many, then the polarity of the blocked polyisocyanate compound (C2) with nonionic hydrophilic group obtained reduces, and sometimes reduces with the intermiscibility of other paint ingredient, therefore, and R3It is preferably the alkylidene of carbon number 1～3, R4And R5It is preferably methyl.
As above-mentioned secondary alcohol (c4), for instance can enumerate: 4-methyl-2-amylalcohol, 5-methyl-2-hexanol, 6-methyl-2-enanthol, 7-methyl-sec-n-octyl alcohol etc., these can be used alone or combine and use two or more.Wherein, after the reaction of the above-mentioned blocked polyisocyanate compound (C1) with nonionic hydrophilic group and above-mentioned secondary alcohol (c4), when part or all of unreacted secondary alcohol (c4) is distilled off, from the viewpoint of being easier to remove this secondary alcohol (c4), more preferably there is more lower boiling 4-methyl-2-amylalcohol.
For the blocked polyisocyanate compound (C2) with nonionic hydrophilic group, from the viewpoint of the stability of the aqueous the 1st pigmented finiss (X) of the present invention, as particularly preferred form, it is possible to enumerate following compound (C2-1) and (C2-2).
There is the blocked polyisocyanate compound (C2-1) of nonionic hydrophilic group
There is the blocked polyisocyanate compound (C2-1) of nonionic hydrophilic group specifically such as to there is the blocked isocyanate base shown in following formula (IV) by what make the explanation of the above-mentioned blocked polyisocyanate compound (C1) with nonionic hydrophilic group is recorded and there is the blocked polyisocyanate compound (C1-1) of non-ionic hydrophilic group and above-mentioned secondary alcohol (c4) reacts and obtains.
[chemical formula 4]
[in formula (IV), R1Represent the alkyl of carbon number 1～12 independently, it is possible to identical, it is also possible to different.]
Now, the R in the blocked isocyanate base in the above-mentioned blocked polyisocyanate compound (C1-1) with nonionic hydrophilic group1At least one party be substituted by the group shown in following formula (VII).
[chemical formula 5]
[in formula (VII), R2、R4And R5Represent the alkyl of carbon number 1～12, R independently3Represent the straight-chain of carbon number 1～12 or the alkylidene of branched.]
It addition, in this case, the blocked polyisocyanate compound obtained has the blocked isocyanate base shown in following formula (I) or the blocked isocyanate base shown in following formula (II).
[chemical formula 6]
[in formula (I), R1、R2、R4And R5Represent the alkyl of carbon number 1～12, R independently3Represent the straight-chain of carbon number 1～12 or the alkylidene of branched.]
[chemical formula 7]
[in formula (II), R2、R3、R4And R5With above-mentioned R2、R3、R4And R5Identical.]
There is no particular limitation in the reaction of the above-mentioned blocked polyisocyanate compound (C1-1) with nonionic hydrophilic group and secondary alcohol (c4), such as can by the R in the blocked isocyanate base in the blocked polyisocyanate compound (C1-1) with nonionic hydrophilic group as long as being1At least one method being substituted by the group shown in above-mentioned formula (VII).Wherein, it is preferable that by the R that heat and decompression etc. will be derived from the blocked polyisocyanate compound (C1-1) with nonionic hydrophilic group1, at least one part or all of alcohol be distilled off to the external promotion reaction of system, the method obtaining having the blocked polyisocyanate compound of the blocked isocyanate base shown in above-mentioned formula (I) or (II) and nonionic hydrophilic group.
As above-mentioned manufacture method, specifically, optionally reduce pressure under at 20～150 DEG C, preferably in the temperature of 75～95 DEG C, with 5 minutes～part or all of above-mentioned alcohol remove by 20 hours, preferably 10 minute～10 hours.If said temperature is too low, the exchange reaction then with alkoxyl in the blocked polyisocyanate compound (C1-1) of nonionic hydrophilic group is slack-off, manufacture efficiency reduces, on the other hand, if said temperature is too high, acutely, curable reduces sometimes, and this is not desired in the decomposition deterioration of the blocked polyisocyanate compound (C2) with nonionic hydrophilic group then obtained.
There is the blocked polyisocyanate compound (C2-2) of nonionic hydrophilic group
Specifically such as can there is the blocked isocyanate base shown in following logical formula V by what make the explanation of the above-mentioned blocked polyisocyanate compound (C1) with nonionic hydrophilic group is recorded and there is the blocked polyisocyanate compound (C1-2) of non-ionic hydrophilic group and above-mentioned secondary alcohol (c4) reacts and obtains it addition, have the blocked polyisocyanate compound (C2-2) of nonionic hydrophilic group.
[chemical formula 8]
[in formula (V), R6And R7Represent the alkyl of carbon number 1～12 independently.]
In this case, the R in the blocked isocyanate base in the above-mentioned blocked polyisocyanate compound (C1-2) with hydrophilic group7Be substituted by the group shown in following formula (VII).
[chemical formula 9]
[in formula (VII), R2、R4And R5Represent the alkyl of carbon number 1～12, R independently3Represent the straight-chain of carbon number 1～12 or the alkylidene of branched.]
In this case, the blocked polyisocyanate compound (C1-2) obtained has the blocked isocyanate base shown in following formula (III).
[chemical formula 10]
[in formula (III), R2、R3、R4And R5With above-mentioned R2、R3、R4And R5Identical, R6Represent the alkyl of carbon number 1～12.]
The reaction of the above-mentioned blocked polyisocyanate compound (C1-2) with nonionic hydrophilic group and secondary alcohol (c4) is not particularly limited, as long as such as can by the R in the blocked isocyanate base in the blocked polyisocyanate compound (C1-2) with nonionic hydrophilic group7The method being substituted by the group shown in above-mentioned formula (VII).Wherein, it is preferable that by the R that heat and decompression etc. will be derived from the blocked polyisocyanate compound (C1-2) with hydrophilic group7, alcohol part or all be distilled off to system external promotion reaction, obtain having the blocked isocyanate base shown in above-mentioned formula (III) and there is the method for blocked polyisocyanate compound (C2-2) of nonionic hydrophilic group.
As above-mentioned manufacture method, specifically, it is adapted at 20～150 DEG C, optionally reduces pressure preferably at the temperature of 75～95 DEG C, through 5 minutes～20 hours, preferably through 10 minutes～10 hours by part or all removing of above-mentioned alcohol.If said temperature is too low, the exchange reaction then with the alkoxyl in the blocked polyisocyanate compound (C1-2) of nonionic hydrophilic group becomes slow, manufacture efficiency reduces, on the other hand, if said temperature is too high, acutely, curable reduces sometimes, and this is not desired in the decomposition deterioration of the blocked polyisocyanate compound (C2) with nonionic hydrophilic group then obtained.
Additionally, from the viewpoint of the reactivity of the blocked polyisocyanate compound (C) with nonionic hydrophilic group obtained and manufacture efficiency, for having in the manufacture of blocked polyisocyanate compound (C2) of nonionic hydrophilic group, the mixing ratio of the above-mentioned blocked polyisocyanate compound (C1) with nonionic hydrophilic group and secondary alcohol (c4), with solid constituent 100 mass parts of the blocked polyisocyanate compound (C1) with nonionic hydrophilic group for benchmark, in the secondary alcohol (c4) scope preferably in 5 mass parts～500 mass parts, it is preferred that in the scope of 10 mass parts～200 mass parts.When lower than 5 mass parts, the response speed with the blocked polyisocyanate compound (C1) of hydrophilic group and secondary alcohol (c4) is sometimes excessively slow.It addition, if it exceeds 500 mass parts, then the concentration of the blocked polyisocyanate compound (C2) with nonionic hydrophilic group generated becomes too low, sometimes manufacture efficiency and reduce.
Additionally, in the reaction of the above-mentioned blocked polyisocyanate compound (C1) with nonionic hydrophilic group and secondary alcohol (c4), in order to adjust the molecular weight of the blocked polyisocyanate compound (C2) with nonionic hydrophilic group, it is possible to carry out above-mentioned removing operation after adding polyol compound in this blocked polyisocyanate compound (C1) with nonionic hydrophilic group and secondary alcohol (c4).
There is compound (C2-1) or the compound (C2-2) stability in water in the blocked polyisocyanate compound (C) of nonionic hydrophilic group excellent especially, supposition is such reason: owing to having nonionic hydrophilic group, therefore more stably exist in water, and then, owing to comprising the alkyl with branched structure, therefore, the polarity of blocked isocyanate base is low, not facile hydrolysis.
In one embodiment, the blocked polyisocyanate compound (C) with nonionic hydrophilic group is the blocked polyisocyanate compound with at least one blocked isocyanate base in the blocked isocyanate base shown in the blocked isocyanate base shown in following formula (I), following formula (II) and the blocked isocyanate base shown in following formula (III).
[chemical formula 11]
[in formula (I), R1、R2、R4And R5Represent the alkyl of carbon number 1～12, R independently3Represent the straight-chain of carbon number 1～12 or the alkylidene of branched.]
[chemical formula 12]
[in formula (II), R2、R3、R4And R5With above-mentioned R2、R3、R4And R5Identical.]
[chemical formula 13]
[in formula (III), R2、R3、R4And R5With above-mentioned R2、R3、R4And R5Identical, R6Represent the alkyl of carbon number 1～12.]
Consider from the viewpoint such as the intermiscibility of other paint ingredient, the aqueous of the present invention the 1st pigmented finiss (X) flatness of coating, distinctiveness, tack, resistance to water and the chipping resistance that are formed, there is the number-average molecular weight of blocked polyisocyanate compound (C) of nonionic hydrophilic group preferably in 600～30, in the scope of 000.From the viewpoint of with the intermiscibility of other paint ingredient and the flatness of film formed by the aqueous the 1st pigmented finiss (X) of the present invention and distinctiveness, the upper limit as above-mentioned number-average molecular weight is more preferably 10,000, more preferably 5,000.It addition, from the viewpoint of the tack of film, resistance to water and the chipping resistance that are formed by the aqueous the 1st pigmented finiss (X) of the present invention, lower limit is more preferably 900, more preferably 1,000.
It addition, the above-mentioned blocked polyisocyanate compound (C) with nonionic hydrophilic group can also mix with surfactant in advance.In this case, from the viewpoint of the stability of the aqueous the 1st pigmented finiss (X) of the present invention, this surfactant is preferably nonionic surfactant.
In the aqueous the 1st pigmented finiss (X) of the present invention, from the viewpoint of the chipping resistance of the film obtained, tack, retouching, weatherability and ethanol petrol resistant, resin solid content quality total amount in the 1st pigmented finiss (X) is for benchmark, the content of the above-mentioned blocked polyisocyanate compound (C) with nonionic hydrophilic group is suitably for 5 mass %～40 mass %, it is preferably 7 mass %～35 mass %, more preferably 10 mass %～30 mass %.
Conductive pigment (D)
Being not particularly limited as conductive pigment (D), as long as electric conductivity can be given to the film formed, the pigment of any shape in particle shape, lamellar, fiber (comprising whisker) shape all can use.Specifically, for instance can enumerate: the conductive carbon such as conductive carbon black, CNT, carbon nano-fiber, the micro-coil of carbon；The metal powders such as silver, nickel, copper, graphite, aluminum, and then, it is possible to enumerate: antimony-doped tin oxide, phosphorus doping stannum oxide, carried out with stannum oxide/antimony surface-coated acicular titanium oxide, stibium oxide, zinc antimonates, tin indium oxide, at the pigment of the surface-coated stannum oxide of whisker etc. of carbon or graphite；The pigment of the coating conductive metal oxide such as stannum oxide or antimony-doped tin oxide of mica surface in lamellar；Pigment etc. contain stannum oxide and phosphorus on TiO 2 particles surface, that there is electric conductivity.These can individually use or combine and use two or more.Wherein, conductive carbon can particularly preferably be used.
From the viewpoint of the electric conductivity of the film obtained and light transmittance, with the resin solid content quality total amount in aqueous the 1st pigmented finiss (X) for benchmark, the content of the above-mentioned conductive pigment in the aqueous the 1st pigmented finiss (X) used in the present invention is suitably for 0.5 mass %～40 mass %, it is preferably 1 mass %～35 mass %, more preferably 3 mass %～30 mass %.
In one embodiment, with the resin solid content quality total amount in aqueous the 1st pigmented finiss (X) for benchmark, the conductive pigment (D) of the aqueous the 1st pigmented finiss (X) the chlorine-free polyolefin-based resins (A) containing 10 mass %～60 mass % that uses in the present invention, the waterborne polyurethane resin (B) of 10 mass %～50 mass %, the blocked isocyanate compounds (C) with nonionic hydrophilic group of 5 mass %～40 mass % and 0.5 mass %～40 mass %.
Other composition
The aqueous the 1st pigmented finiss (X) used in the present invention with above-mentioned chlorine-free polyolefin-based resins (A), specific waterborne polyurethane resin (B), there is the blocked polyisocyanate compound (C) of non-aqueous hydrophilic group, conductive pigment (D) for required composition, the resinous principles such as the blocked polyisocyanate compound beyond containing hydroxy acryl acid resin, hydroxyl group containing polyester resin, composition (C), melmac, phenolic resin, polycarbonate resin and epoxy resin can be suitable for further.
Hydroxy acryl acid resin can use the hydroxy acryl acid resin of the water solublity known per se or water dispersible used in conventional water paint.Hydroxy acryl acid resin such as by making hydroxyl polymerism unsaturated monomer and can manufacture with method copolymerization such as the method that other polymerism unsaturated monomer of this hydroxyl polymerism unsaturated monomer copolymerization had both been known by himself, such as polymerisation in solutions.
Hydroxyl polymerism unsaturated monomer is the compound being respectively provided with more than 1 hydroxyl and polymerism unsaturated bond in 1 molecule, for instance can enumerate: the monoesters compound of the glycol such as (methyl) Hydroxyethyl Acrylate, (methyl) hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate and polyethyleneglycol (methyl) acrylate and acrylic or methacrylic acid；The monoesters compound making 6-caprolactone sour with above-mentioned polyhydric alcohol and acrylic or methacrylic carries out the compound etc. of ring-opening polymerisation.
Can suitably select according to the desired characteristic of hydroxy acryl acid resin with other polymerism unsaturated monomer of hydroxyl polymerism unsaturated monomer copolymerization and use.The specific embodiment of this monomer is set forth below.These can individually use or combine and use two or more.
(i) (methyl) acrylic acid alkyl or cycloalkyl ester: such as (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) tert-butyl acrylate, the just own ester of (methyl) acrylic acid, (methyl) n-octyl, (methyl) 2-EHA, (methyl) acrylic acid ester in the ninth of the ten Heavenly Stems, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) stearyl acrylate base ester, (methyl) acrylic acid iso stearyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic methyl cyclohexyl, (methyl) t-butylcyclohexyl ester, (methyl) acrylic acid cyclo-dodecyl ester, (methyl) acrylic acid tricyclodecyl etc..
(ii) there is the polymerism unsaturated monomer of isobornyl: such as (methyl) isobornyl acrylate etc..
(iii) there is the polymerism unsaturated monomer of adamantyl: such as (methyl) acrylic acid adamantane esters etc..
(iv) there is the polymerism unsaturated monomer of tricyclic decenyl: such as (methyl) acrylic acid tricyclodecenyl esters etc..
(v) polymerism unsaturated monomer containing aromatic rings: such as (methyl) benzyl acrylate, styrene, α-methyl styrene, vinyltoluene etc..
(vi) there is the polymerism unsaturated monomer of alkoxysilyl: such as vinyltrimethoxy silane, VTES, vinyl three (2-methoxy ethoxy) silane, γ-(methyl) acryloxypropyl trimethoxy silane, γ-(methyl) acryloxypropyl triethoxysilane etc..
(vii) there is the polymerism unsaturated monomer of fluoro-alkyl: such as (methyl) perfluoroalkyl acrylate such as (methyl) perfluoroethyl butyl ethyl ester, (methyl) perfluoroethyl octyl group ethyl ester；Fluoroolefin etc..
(viii) there is the polymerism unsaturated monomer of the optical polymerism functional groups such as Maleimido.
(ix) vinyl compound: such as NVP, ethylene, butadiene, chlorobutadiene, propionate, vinyl acetate etc..
The polymerism unsaturated monomer of (x) phosphorous acidic group: such as 2-acryloyl-oxyethyl phosphate ester acid, 2-methacryloxyethyl phosphate ester acid, 2-acryloxypropyl phosphate ester acid, 2-methacryloxypropyl acid phosphate are cruel etc..
(xi) carboxylic polymerism unsaturated monomer: such as (methyl) acrylic acid, maleic acid .beta.-methylacrylic acid, P-carboxy ethyl acrylates etc..
(xii) nitrogenous polymerism unsaturated monomer: such as (methyl) acrylonitrile, (methyl) acrylamide, (methyl) acrylic acid N, N-dimethylamino ethyl ester, (methyl) acrylic acid N, the addition product etc. of N-diethylamino ethyl ester, N, N-dimethylaminopropyl (methyl) acrylamide, di-2-ethylhexylphosphine oxide (methyl) acrylamide, ethylenebis (methyl) acrylamide, 2-(methacryloxy) ethyl-trimethyl salmiac, (methyl) glycidyl acrylate and amine.
(xiii) 1 molecule has the polymerism unsaturated monomer of at least 2 polymerism unsaturated groups: such as, (methyl) allyl acrylate, 1,6-hexanediol two (methyl) acrylate etc..
(xiv) the polymerism unsaturated monomer containing epoxy radicals: such as (methyl) glycidyl acrylate, (methyl) propenoic acid beta-methylglycidyl esters, (methyl) acrylic acid 3,4-epoxycyclohexanecarboxylate, (methyl) acrylic acid 3,4-epoxycyclohexyl ethyl ester, (methyl) acrylic acid 3,4-epoxycyclohexyl propyl ester, allyl glycidyl ether etc..
(xv) there is (methyl) acrylate of the polyoxyethylene chain that molecular end is alkoxyl.
(xvi) there is sulfonic polymerism unsaturated monomer: such as 2-acrylamido-2-methyl propane sulfonic acid, (methyl) acrylic acid 2-sulphur ethyl ester, allyl sulphonic acid, 4-styrene sulfonic acid etc.；The sodium salt of these sulfonic acid and ammonium salt etc..
(xvii) there is the polymerism unsaturated monomer of ultraviolet-absorbing functional group: such as 2-hydroxyl-4-(3-methacryloxy-2-hydroxy propyloxy group) benzophenone, 2-hydroxyl-4-(3-acryloxy-2-hydroxy propyloxy group) benzophenone, 2,2 '-dihydroxy-4-(3-methacryloxy-2-hydroxy propyloxy group) benzophenone, 2,2 '-dihydroxy-4-(3-acryloxy-2-hydroxy propyloxy group) benzophenone, 2-(2 '-hydroxyl-5 '-methaciylyloxyethylphenyl)-2H-benzotriazole etc..
null(xviii) light stability polymerism unsaturated monomer: such as 4-(methyl) acryloxy-1,2,2,6,6-pentamethvl、4-(methyl) acryloxy-2,2,6,6-tetramethyl piperidine、4-cyano group-4-(methyl) Acryloyl amino-2,2,6,6-tetramethyl piperidine、1-(methyl) acryloyl group-4-(methyl) Acryloyl amino-2,2,6,6-tetramethyl piperidine、1-(methyl) acryloyl group-4-cyano group-4-(methyl) Acryloyl amino-2,2,6,6-tetramethyl piperidine、4-Fructus Crotonis acyloxy-2,2,6,6-tetramethyl piperidine、4-crotonocyl amino-2,2,6,6-tetramethyl piperidine、1-crotonocyl-4-Fructus Crotonis acyloxy-2,2,6,6-tetramethyl piperidine etc..
(xix) there is the polymerism unsaturated monomer of carbonyl: such as acrylic aldehyde, N-[2-(2-methyl-4-oxopentyl), diacetone methacrylamide, acetoacetoxyethyl methacrylate, formoxyl styrene, have 4～7 carbon atoms vinyl alkyl ketone (such as, ethenyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) etc..
(xx) there is the polymerism unsaturated monomer of anhydride group: such as maleic anhydride etc., itaconic anhydride, citraconic anhydride etc..
For hydroxy acryl acid resin, generally be suitable for hydroxyl value in the scope of 10～150, be particularly suitable in the scope of 50～100, acid number is adapted at less than 60, be particularly suitable for below 50, weight average molecular weight is adapted in the scope of 1000～100000, is particularly suitable in the scope of 2000～60000.
Additionally, in this manual, the value that the weight average molecular weight of above-mentioned hydroxy acryl acid resin and the number-average molecular weight of hydroxyl group containing polyester resin described later and melmac described later are tried to achieve for are scaled the molecular weight of polystyrene according to the retention time (maintenance capacity) of the known polystyrene standard of the molecular weight recorded in identical conditions the retention time (maintenance capacity) using gel permeation chromatography (GPC) to record.Specifically, use " HLC-8120GPC " (trade name, Dong Cao company manufactures) as gel permeation chromatography device, use " TSKgelG4000HXL ", " TSKgelG3000HXL ", " TSKgelG2500HXL " and " TSKgelG2000HXL " (trade name, it is Dong Cao company to manufacture) amount to 4 as chromatographic column, differential refraction rate is used to be counted as detector, can at mobile phase: oxolane, measure temperature: 40 DEG C, flow velocity: measure when 1mL/min.
In the aqueous the 1st pigmented finiss (X) used in the present invention, from the viewpoint of the chipping resistance of the film obtained, tack, retouching, weatherability and ethanol petrol resistant, with the total resin solid content amount in the 1st pigmented finiss (X) for benchmark, the consumption that makes during hydroxy acryl acid resin is used to be suitably for 5 mass %～35 mass %, it is preferred to 10 mass %～25 mass %.
Hydroxyl group containing polyester resin can use the hydroxyl group containing polyester resin of the water solublity known per se or water dispersible used in current water paint, for instance can obtain by making polyprotic acid and polyhydric alcohol carry out esterification by method known per se when hydroxyl is excessive.Polyprotic acid is the compound in 1 molecule with more than 2 carboxyls, such as can enumerate: phthalic acid, M-phthalic acid, p-phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, Pyromellitic Acid, itaconic acid, adipic acid, decanedioic acid, Azelaic Acid, dodecanedioic acid, dimeric dibasic acid, humic acids, succinic acid, HET acid and their acid anhydride etc..Polyhydric alcohol is the compound in 1 molecule with more than 2 hydroxyls, such as can enumerate: ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, butanediol, hexanediol, 2-ethyl-2-butyl-1,3-PD, cyclohexanedimethanol, trimethylolethane, trimethylolpropane, tetramethylolmethane, dipentaerythritol, Sorbitol etc..The introducing of hydroxyl such as can be carried out by being simultaneously used in the polyhydric alcohol in 1 molecule with more than 3 hydroxyls.It addition, as polyester resin, it is possible to use by the fatty acid modified polyester resin that the fatty acids etc. such as soya fatty acid, Castor Oil Fatty Acid, dehydrated castor oil fatty acid modifiy excessively.It addition, polyester resin can also be modified with epoxides such as butyl glycidyl base ether, alkyl phenyl glycidyl ethers, glycidyl neodecanoate.
For hydroxyl group containing polyester resin, usual hydroxyl value is adapted in the scope of 10mgKOH/g～160mgKOH/g, is particularly suitable in the scope of 50mgKOH/g～85mgKOH/g, acid number is adapted at below 50mgKOH/g, be particularly suitable in the scope of 1mgKOH/g～30mgKOH/g, number-average molecular weight is adapted at 1,000～20, in the scope of 000, it is particularly suitable for 1, in the scope of 300～10,000.
In the aqueous the 1st pigmented finiss (X) used in the present invention, from the viewpoint of the chipping resistance of the film obtained, tack, retouching, weatherability and ethanol petrol resistant, with the total resin solid content amount in the 1st pigmented finiss (X) for benchmark, the consumption that makes during hydroxyl group containing polyester resin is used to be suitably for 2 mass %～20 mass %, it is preferred to 5 mass %～15 mass %.
End-blockingization polyisocyanate compounds beyond composition (C) is that the NCO to polyisocyanate compounds adds end-capping reagent and obtains, and, the blocked polyisocyanate compound generated by adding is stable at normal temperatures, but during preferably in sintering temperature (normally about 80 DEG C～about 200 DEG C) heated to film, end-capping reagent can dissociate and again generate free NCO.As the end-capping reagent meeting such essential condition, for instance can enumerate: the end-capping reagent such as phenols, lactams, alcohols, ethers, oximes, active methylene group class, thio-alcohol, acid amide-type, acid imide class, amine, imidazoles, pyrazoles.
As melmac, it is particularly preferred to carried out the alkyl etherified melamine resin of etherificate with alkyl such as methyl, ethyl, normal-butyl, isobutyl group, hexyl, 2-ethylhexyls.These melmacs can have methylol, imino group etc. further.Number-average molecular weight that melmac is generally preferable to be had in the scope of 500～5,000, the number-average molecular weight particularly preferably having in the scope of 800～3,000.
The aqueous used in the present invention the 1st pigmented finiss (X) can contain the additive for coatings etc. such as coloring pigment, extender pigment, organic solvent, silane coupler, curing catalysts, viscosifier, defoamer, surface conditioner, coalescents further.
As coloring pigment, for instance can enumerate: titanium oxide, white carbon black, chrome yellow, loess, yellow iron oxide, hansa yellow, pigment yellow, chrome orange, molybdate red, forever solid orange, umber, permanent bordeaux, bright carmine, Fast violet, Methyl Violet Lake, ultramarine, Prussian blue, cobalt blue, phthalocyanine blue, naphthol green, naphthol green, aluminum cream.These can individually use or combine and use two or more.
From the viewpoint of the light transmittance of the film obtained and retouching property, when the aqueous the 1st pigmented finiss (X) used in the present invention is containing above-mentioned coloring pigment, with the resin solid content quality total amount in aqueous the 1st pigmented finiss (X) for benchmark, the content of this coloring pigment is adapted in the scope of 1 mass %～180 mass %, in scope preferably in 2 mass %～140 mass %, it is preferred that in the scope of 4 mass %～130 mass %.
As extender pigment, for instance can enumerate: Talcum, silicon dioxide, calcium carbonate, barium sulfate, zinc white (zinc oxide) etc..These can individually use or combine and use two or more.
From the viewpoint of the light transmittance of the film obtained and chipping resistance, when the aqueous the 1st pigmented finiss (X) used in the present invention is containing above-mentioned extender pigment, with the resin solid content quality total amount in aqueous the 1st pigmented finiss (X) for benchmark, the content of this extender pigment is 1 mass %～150 mass %, it is preferably 5 mass %～130 mass %, it is preferred that in the scope of 10 mass %～110 mass %.
It is not particularly limited as organic solvent, as long as above-mentioned resinous principle such as can being mixed and dissolves or scattered organic solvent, it is possible to enumerates such as Aliphatic hydrocarbon solvents, aromatic hydrocarbon solvent, alcohols solvent, esters solvent, ketones solvent equal solvent.
As silane coupler, such as can enumerate: 2-(3, 4 epoxycyclohexyls) ethyltrialkoxysilanes, 3-glycidoxypropyl group trialkoxy silane, 3-glycidoxypropyl dialkoxy silicane, N-2-(amino-ethyl)-3-amino propyl methyl dialkoxy silicane, N-2-(amino-ethyl)-3-aminopropyltrialkoxy silanes, 3-aminopropyltrialkoxy silanes, 3-amino propyl methyl dialkoxy silicane, 3-mercaptopropyi methyl dioxane TMOS, 3-mercaptopropyi trialkoxy silane, N-phenyl-3-aminopropyltrialkoxy silanes, 3-ureidopropyltrialkoxysilane, 3-chloropropyl trialkoxy silane, double, two (trialkoxysilyl propyl group) tetrasulfide, 3-isocyanates propyl trialkoxy silane etc..These can individually use or combine and use two or more.
The solid component concentration of aqueous the 1st pigmented finiss (X) is preferably generally 20 mass %～70 mass %, more preferably 30 mass %～60 mass %, more preferably 35 mass %～60 mass %.
The application of the aqueous the 1st pigmented finiss (X) used in the present invention is not particularly limited, for instance can pass through the coating process such as aerial spraying application, airless spraying application, rotary-atomizing application, curtain painting application and form wet coating.In these coating process, it is also possible to optionally apply electrostatic.Wherein, it is particularly preferred to aerial spraying application.The painting loading amount of aqueous the 1st pigmented finiss (X) is preferably set to be generally 1 μm～20 μm based on the thickness of cured coating film, is in particular 3 μm～amount of 15 μm.Application aqueous in like fashion the 1st pigmented finiss (X), can form the 1st painted film.
From the viewpoint of the chipping resistance of the film formed, tack, retouching and weatherability, application aqueous the 1st pigmented finiss (X) the cured coating film making it solidify and obtaining are suitable for lower than 1% in the average transmittance at wavelength 360nm～420nm place when thickness is 5 μm, are particularly suitable for lower than 0.5%.Average transmittance can be set by the amount etc. of pigment contained in the thickness of adjustment cured coating film and average transmittance.
At this, above-mentioned thickness is that the cured coating film of the 5 μm average transmittance at wavelength 360nm～420nm place can be measured by following method.
First, on polyfluortetraethylene plate to solidify time coating thickness be 5 μm mode application aqueous the 1st pigmented finiss (X) and make it solidify.Then, film solidification obtained is peeled off and is reclaimed, and uses the average transmittance of the scope of spectrophotometer measurement wavelength 360nm～420nm.As above-mentioned spectrophotometer, for instance " SolidSpec-3700 " (trade name, Shimadzu Seisakusho Ltd. manufactures) etc. can be used.
Operation (2)
Application aqueous the 2nd pigmented finiss (Y) on above-mentioned 1st painted film.
The solid constituent containing ratio of above-mentioned 1st painted film can pass through such as to preheat (preheating), air blast etc. before application aqueous the 2nd pigmented finiss (Y) and adjust, but in the present invention, even if not preheating after application aqueous the 1st pigmented finiss (X), it is possible to obtain the multilayer film that chipping resistance, tack, retouching, weatherability and ethanol petrol resistant are excellent.When not preheating, after application aqueous the 1st pigmented finiss (X), it is preferable that room temperature about 20 DEG C～about 35 DEG C) under stand (placement) 30 seconds～about 5 minutes.This prevents the mixed layer of the 1st painted film and the 2nd painted film.
When preheating, this preheat generally can by being in about 50 DEG C～about 110 DEG C in drying oven, be preferably in about 60 DEG C～temperature of about 80 DEG C under the coated article of direct or indirect heating institute application within about 1 minute～30 minutes, carry out.
It addition, generally can by the air blown of room temperature or heating to the temperature of about 25 DEG C～about 80 DEG C is carried out above-mentioned air blast to the application face of coated article.
Aqueous the 2nd pigmented finiss (Y)
As the aqueous the 2nd pigmented finiss (Y) used in the present invention, for instance commonly used pigmented finiss known per se in the application of car body can be used.
Aqueous the 2nd pigmented finiss (Y) generally can by preparing mixing dispersions such as matrix resin, cross-linking agent and pigment in an aqueous medium.
As matrix resin, for instance resin containing carboxyl and hydroxyl is preferably used.Kind as matrix resin, it is possible to enumerate: acrylic resin, polyester resin, polyether resin, polycarbonate resin, polyurethane resin etc..
Preferably the carboxyl in the resin containing carboxyl and hydroxyl is neutralized.This neutralization carries out preferably in use alkaline matter before mixing with cross-linking agent etc..
As the alkaline matter for neutralizing, for instance can enumerate: ammonia；The primary monoamines such as ethamine, propylamine, butylamine, benzylamine, monoethanolamine, neopentyl alcohol amine, 2-aminopropanol, 3-aminopropanol；Diethylamine, diethanolamine, two just or the secondary monoamine such as diisopropanolamine (DIPA), N-methylethanolamine, N-ehtylethanolamine；The tertiary monoamines such as N, N-dimethylethanolamine, trimethylamine, triethylamine, Tris(isopropylamine)., methyl diethanolamine；The polyamines such as Diethylenetriamine, Hydroxy-ethylamino ethamine, ethylamino ethamine, methylaminopropylamine, these can individually use or combine and use two or more.
With containing the carboxyl in carboxyl and hydroxy resin for benchmark, make consumption generally preferable in the scope of 0.1 equivalent～1.5 equivalent for the alkaline matter that neutralizes, it is particularly preferred in the scope of 0.3 equivalent～1.2 equivalent.
Consider from the viewpoint such as water dispersible, acid number that matrix resin is generally preferable to be had in the scope of 10mgKOH/g～150mgKOH/g, the acid number particularly preferably having in the scope of 30mgKOH/g～100mgKOH/g.It addition, consider from the viewpoint such as curable, hydroxyl value that matrix resin is generally preferable to be had in the scope of 10mgKOH/g～150mgKOH/g, the hydroxyl value particularly preferably having in the scope of 30mgKOH/g～100mgKOH/g.
And then, consider from viewpoints such as weather resisteants, when matrix resin is acrylic resin, generally preferable have in the scope of 3000～100000 number-average molecular weight, the number-average molecular weight that particularly preferably has in the scope of 5000～50000, and when matrix resin is polyester resin, it is usually preferred to there is the number-average molecular weight in the scope of 500～50000, the number-average molecular weight particularly preferably having in the scope of 3000～30000.
When using acrylic resin containing carboxyl and hydroxyl as matrix resin, it is possible to use be polymerized by emulsion when there is dispersion stabilizer and the acrylic resin containing carboxyl and hydroxyl that manufactures.
When the acrylic resin manufactured above by emulsion polymerization, it is usually preferred to there is the acrylic resin of the number-average molecular weight of more than 100000, particularly preferably there is the acrylic resin of number-average molecular weight in the scope of 200000～2000000.
The dispersion stabilizer used in being polymerized as emulsion, except ionic species surfactant or anionic based surfactants, also can be suitable for the water-base resins such as the acrylic resin that use acid number is about 10mgKOH/g～150mgKOH/g and number-average molecular weight is about 5000～30000.
Emulsion polymerization can be undertaken by method known per se.
As matrix resin, wherein, can obtain, by the acrylic emulsion of the multistage polymerization method manufacture being copolymer composition with carboxylic unsaturated monomer, the aqueous the 2nd pigmented finiss (Y) that painting operation is excellent, therefore preferably.That is, monomer mixture first by the composition being entirely free of or being practically free of (being generally below 3 mass % in whole monomers) carboxylic unsaturated monomer carries out polyreaction, the monomer mixture being then used by the composition containing (being generally 5 mass %～30 mass % in whole monomers) carboxylic unsaturated monomer carries out polyreaction, thus obtain acrylic emulsion, this acrylic emulsion is by using the neutralization of alkaline matter, there is viscosity and manifest (viscosity) effect, the aqueous the 2nd pigmented finiss (Y) that the painting operations such as sag resistance are excellent can be obtained, therefore preferably.
As cross-linking agent, it is possible to use selected from such as melmac, blocked polyisocyanate compound, water dispersible blocked polyisocyanate compound etc. can with at least one in the cross-linking agent of hydroxyl reaction.
Matrix resin in aqueous the 2nd pigmented finiss (Y) and the mixing ratio of cross-linking agent are with the total solid constituent amount of two-component for benchmark, matrix resin is preferably generally in the scope of 60 mass %～100 mass %, be particularly preferably the scope of 65 mass %～95 mass % in, be particularly preferably in the scope of 70 mass %～90 mass % further, cross-linking agent is preferably generally in the scope of 0 mass %～40 mass %, it is particularly preferably in the scope of 5 mass %～35 mass %, is particularly preferably further in the scope of 10 mass %～30 mass %.
As pigment, it does not have limit especially, for instance can be suitable for using mineral-type and the coloring pigment of organic pigment, extender pigment and bright pigment etc..As above-mentioned coloring pigment, for instance can enumerate: titanium oxide, zinc white, white carbon black, cadmium red, chrome vermillion, chrome yellow, chromium oxide, Prussian blue, cobalt blue, AZOpigments, phthalocyanine color, quinacridone pigment, isoindoline pigment, intellectual circle's series pigments, pigment etc..As above-mentioned extender pigment, it is possible to enumerate: Talcum, clay, Kaolin, Barium monoxide, barium sulfate, brium carbonate, calcium carbonate, silicon dioxide and aluminium oxide are white.As above-mentioned bright pigment, it is possible to enumerate: aluminium powder, mica powder, by the coating mica powder etc. of titanium oxide.
Adding up to benchmark with the solid constituent of matrix resin and cross-linking agent, the use level of pigment is generally in the scope of 0.1 mass %～200 mass %, it is particularly preferred in the scope of 1 mass %～100 mass %.
Aqueous the 2nd pigmented finiss (Y) can optionally further suitably use curing catalysts, dispersant, sagging inhibitor, defoamer, thickening agent, UV absorbent, light stabilizer, surface conditioner, antioxidant etc..
The generally preferable 15 mass %～65 mass % of the aqueous the 2nd pigmented finiss (Y) the nonvolatile component concentration when application, its independent film can be the film of opaque or transparent three-dimensional tone or metal tone.In this manual, opaque film refers to the film lower than 5% of the light transmittance in the cured coating film of 20 μm of independent coating film, and transparent coating refers to the film more than 5% of the light transmittance in the above-mentioned cured coating film of 20 μm.
Aqueous the 2nd pigmented finiss (Y) such as can by aerial spraying, airless spraying, rotary-atomizing application etc. and optionally apply electrostatic and carry out application and make to be usually based on the thickness of cured coating film 5 μm～30 μm, particularly 10 μm～25 μm.
In the present invention, application aqueous the 2nd pigmented finiss (Y) on the 1st painted film, then transparent paint coating (Z), but the 2nd painted film that application aqueous the 2nd pigmented finiss (Y) is obtained can also be carried out predrying at the temperature of 50 DEG C～about 100 DEG C at the Optional of transparent paint coating (Z).
Predrying by this, the volatile ingredient in the 2nd painted film can be made to volatilize to a certain extent.
By above-mentioned predrying, film is dry solidification to a certain extent, therefore, as transparent paint coating (Z) on the 2nd painted film, even if the infiltration such as solvent contained in this film or low-molecular-weight resin composition diffuses in the 2nd painted film, also can suppressing the decrease in viscosity of the 2nd painted film, the flowing again of bright pigment etc. when can suppress to use bright pigment etc., thus metallic dot etc. can be prevented.
Especially, the method of forming layered coating film of the present invention, when forming high white pearlescent tone multilayer film, can be carried out as the white substrate coating containing Chinese white of the 2nd pigmented finiss (Y) and the interference pearly-lustre color base primer containing mica powder by application successively.After this white substrate coating of application, it is possible to do not carry out predrying or carry out predrying at the temperature of 50 DEG C～about 100 DEG C, it is also possible to being sintered at the temperature of 100 DEG C～about 140 DEG C.
Operation (3)
As above the painted film of aqueous the 2nd formed by aqueous the 2nd pigmented finiss (Y) is coated with clear dope (Z).
Clear dope (Z)
As clear dope, such as can use containing the resinous principle such as matrix resin, cross-linking agent and organic solvent or water etc. and coordinate the organic solvent system of the additive for coatings such as curing catalysts, UV absorbent, light stabilizer, painting face regulator, rheology control agent, antioxidant, defoamer, wax or the Thermocurable coating of water system further, and it has the transparency of coating film degree under the transparent coating identification that can pass through to be formed.
As above-mentioned matrix resin, such as can enumerate: the resins such as the acrylic resin of the reactive functional groups of at least one containing hydroxyl, carboxyl, silanol group, epoxy radicals etc., polyester resin, alkyd resin, fluororesin, urethane resin, containing silicone resin, it is particularly preferred to hydroxy acryl acid resin.
Hydroxy acryl acid resin (K)
Hydroxy acryl acid resin (K) can pass through to utilize conventional method to make the monomer component copolymerization being made up of other polymerism unsaturated monomer of (k1) hydroxyl polymerism unsaturated monomer and (k2) manufacture.
Hydroxyl polymerism unsaturated monomer (k1) is the compound in 1 molecule with 1 hydroxyl and 1 polymerism unsaturated bond.
As hydroxyl polymerism unsaturated monomer (k1), it is possible to enumerate: polymerism unsaturated monomer (k1-1) containing secondary hydroxyl and the polymerism unsaturated monomer (k1-2) of hydroxyl (not including secondary hydroxyl).
As the polymerism unsaturated monomer (k1-1) containing secondary hydroxyl, for instance can enumerate: the carbon number of the alkyl of the ester moieties such as (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 2-hydroxybutyl, (methyl) acrylic acid 3-hydroxybutyl is 2～8, particularly 3～6, further particularly 3 or 4 the polymerism unsaturated monomer with secondary hydroxyl；The addition product etc. of (methyl) acrylic acid and the compound (HexionSpecialtyChemicals company manufactures, glycidyl neodecanoate for such as CarduraE10, trade name) containing epoxy radicals.Wherein, particularly from the viewpoint of the chipping resistance of the multilayer film obtained, tack, retouching, weatherability and ethanol petrol resistant, it is preferable that (methyl) acrylic acid 2-hydroxy propyl ester.
Above-mentioned monomer (k1-1) can use a kind or combination use two or more.
The polymerism unsaturated monomer (k1-2) that hydroxyl (does not include secondary hydroxyl) is the compound in 1 molecule with 1 hydroxyl (not including secondary hydroxyl) and 1 polymerism unsaturated bond.
As this monomer, for instance can enumerate: the monoesters compound (not including the material with secondary hydroxyl) of the dihydroxylic alcohols of (methyl) acrylic acid such as (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 4-hydroxybutyl and carbon number 2～10；By making 6-caprolactone carry out ring-opening polymerization and modified hydroxyl monomer (not including the material with secondary hydroxyl) etc..
Ring-opening polymerization is carried out and modified hydroxyl monomer as making 6-caprolactone, market sale product can be used, as market sale product, such as can enumerate: " PlaccelFA-1 ", " PlaccelFA-2 ", " PlaccelFA-3 ", " PlaccelFA-4 ", " PlaccelFA-5 ", " PlaccelFM-1 ", " PlaccelFM-2 ", " PlaccelFM-3 ", " PlaccelFM-4 ", " PlaccelFM-5 " (being Diacel chemistry (strain) above to manufacture, trade name) etc..
Above-mentioned monomer (k1-2) can use a kind or combination use two or more.
Other polymerism unsaturated monomer (k2) is the monomer beyond above-mentioned hydroxyl polymerism unsaturated monomer (k1), specifically has the compound of 1 polymerism unsaturated bond in 1 molecule.The specific embodiment of unsaturated monomer (k2) is enumerated in following (1)～(7).
(1) the polymerism unsaturated monomer containing acidic group
Polymerism unsaturated monomer containing acidic group is the compound in 1 molecule with 1 acidic group and 1 polymerism unsaturated bond.As this monomer: such as can enumerate: carboxyl group-containing monomers such as (methyl) acrylic acid .beta.-methylacrylic acid, itaconic acid, maleic acid and maleic anhydrides；The monomer containing sulfonic acid such as vinyl sulfonic acid, (methyl) sulfoethyl acrylate；The acid phosphatase esters monomers etc. such as 2-(methyl) acryloyl-oxyethyl acid phosphoric acid ester, 2-(methyl) acryloxypropyl acid phosphoric acid ester, 2-(methyl) acryloxy-3-chloropropyl acid phosphoric acid ester, 2-methaciylyloxyethylphenyl phosphoric acid.These monomers can use one kind or two or more.
(2) carboxylate of the monohydric alcohol of acrylic or methacrylic acid and carbon number 1～20
Specifically, can enumerate: (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) propyl acrylate, butyl acrylate, (methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) tert-butyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) Isooctyl acrylate monomer, the different lima bean base ester of (methyl) acrylic acid, (methyl) stearyl acrylate base ester, (Osaka Organic Chemical Industry company manufactures (methyl) acrylic acid iso stearyl ester, trade name), (methyl) lauryl acrylate, (methyl) tridecyl acrylate, (methyl) stearyl acrylate base ester, (methyl) acrylic acid tetrahydro furfuryl ester, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate.
In the carboxylate of aforesaid propylene acid or the monohydric alcohol of methacrylic acid and carbon number 1～20, from the viewpoint of the raising of finished appearance and have both hardness of film, can be suitable for using the polymerism unsaturated monomer (k2-1) of the ester ring type alkyl containing carbon number 6～20.
Representative embodiment as the ester ring type alkyl of carbon number 6～20, it is possible to enumerate: cyclohexyl, ring octyl group, cyclo-dodecyl, isobornyl, adamantyl and tricyclodecyl etc..
Specific embodiment as unsaturated monomer (k2-1), for instance can enumerate: (methyl) acrylate base esters such as (methyl) cyclohexyl acrylate, (methyl) acrylic acid-4-methylcyclohexyl methyl ester, (methyl) acrylic acid-4-ethylcyclohexyl methyl ester, (methyl) acrylic acid-4-methoxycyclohexyl methyl ester, (methyl) t-butylcyclohexyl ester, (methyl) acrylic acid ring monooctyl ester, (methyl) acrylic acid cyclo-dodecyl ester；The polymerism unsaturated monomer etc. containing bridge ester ring type alkyl such as (methyl) isobornyl acrylate, (methyl) acrylic acid tricyclodecyl, (methyl) acrylic acid adamantane esters, (methyl) acrylic acid-3,5-dimethyladamantane base ester, (methyl) acrylic acid-3-Fourth Ring ester in the last of the ten Heavenly stems.Wherein, particularly from the viewpoint of the chipping resistance of the multilayer film obtained, tack, retouching, weatherability and ethanol petrol resistant, it is preferable that (methyl) isobornyl acrylate.
When using unsaturated monomer (k2-1), its mixing ratio preferably with respect to the total amount of monomer component in the scope of 20 mass %～45 mass %, it is particularly preferred in the scope of 30 mass %～40 mass %.
(3) the polymerism unsaturated monomer containing alkoxysilyl
Specifically, it is possible to enumerate: vinyltrimethoxy silane, VTES, acryloyl-oxyethyl trimethoxy silane, methacryloxyethyl trimethoxy silane, acryloxypropyl trimethoxy silane, methacryloxypropyl trimethoxy silane, acryloxypropyl triethoxysilane, methacryloxypropyl, vinyl three ('beta '-methoxy ethyoxyl) silane etc..As the wherein preferred polymerism unsaturated monomer containing alkoxysilyl, it is possible to enumerate: vinyltrimethoxy silane, γ-acryloxypropyl trimethoxy silane, γ-methacryloxypropyl trimethoxy silane etc..
By using the polymerism unsaturated monomer containing alkoxysilyl as constituent, beyond the cross-bond of hydroxyl-removal and NCO, the cross-bond also generating the reaction by alkoxysilyl condensation reaction each other and alkoxysilyl and hydroxyl and formed, therefore can improve curable.
When using the polymerism unsaturated monomer containing alkoxysilyl as constituent, relative to the total amount of monomer component, in its mixing ratio scope preferably in 1 mass %～20 mass %, it is particularly preferred in the scope of 1 mass %～10 mass %.
(4) fragrance same clan vinyl monomer
Specifically, it is possible to enumerate: styrene, α-methyl styrene, vinyltoluene etc..
By using aromatic series Type of Collective unsaturated monomer as constituent, the glass transition temperature of the resin obtained improves, and additionally can obtain high index of refraction and hydrophobic film, can obtain improving by improving the gloss of film the effect of finished appearance.
When using aromatic series Type of Collective unsaturated monomer as constituent, relative to the total amount of monomer component, in its mixing ratio scope preferably in 5 mass %～30 mass %, it is particularly preferred in the scope of 10 mass %～20 mass %.
(5) the polymerism unsaturated monomer containing glycidyl
Polymerism unsaturated monomer containing glycidyl is the compound in 1 molecule with 1 glycidyl and 1 polymerism unsaturated bond, specifically, it is possible to enumerate: glycidyl acrylate, glycidyl methacrylate etc..
(6) containing the compound of the nitrogen atom of polymerism unsaturated bond
Such as can enumerate: acrylamide, Methacrylamide, DMAA, N, N-dimethyl propyl acrylamide, N-butoxy methyl acrylamide, N hydroxymethyl acrylamide, N-methylol methacrylamide, N-[2-(2-methyl-4-oxopentyl), N, N-dimethyl aminoethyl (methyl) acrylate, vinylpyridine, vinyl imidazole, acrylonitrile, methacrylonitrile etc..
(7) other vinyl compound
Such as can enumerate: vinyl acetate, propionate, vinyl chloride, tertiary ethylene carbonate etc..As tertiary ethylene carbonate, it is possible to enumerate: as " VEOVA9 ", " VEOVA10 " (be trade name above, JapanEpoxyResin (strain) manufacture) etc. of market sale product.
Polymerism unsaturated monomer (k2) as other, it is possible to use the monomer shown in one kind or two or more above-mentioned (1)～(7).
From the viewpoint of the finished appearance of film and curable, the weight average molecular weight of hydroxy acryl acid resin (K) is preferably 5000～18000, it is particularly preferred to be 8000～15000.
From the viewpoint of the curable of film and finished appearance, the glass transition temperature of hydroxy acryl acid resin (K) is preferably-25 DEG C～20 DEG C, it is particularly preferred to for-15 DEG C～10 DEG C.
At this, glass transition temperature (Tg) can be calculated by following equation.
1/Tg (° K)=(W1/T1)+(W2/T2)+
Tg (DEG C)=Tg (° K)-273
In various, weight %, the T1 of each monomer that use in W1, W2, expression copolymerization, T2, represent the Tg (° K) of the homopolymer of monomer respectively.It addition, T1, T2, be based on PolymerHandBook (SecondEdition, the J.Brandup E.H.Immergut volume) value obtained.
Additionally, glass transition temperature (DEG C) when the Tg of the homopolymer of monomer is not clear and definite is static glass transition temperature, such as use differential scanning calorimeter " DSC-50Q type " (Shimadzu Seisakusho Ltd.'s system, trade name), sample is taked from measuring cup, after carrying out vacuum draw and removing solvent completely, with the programming rates of 3 DEG C/min-100 DEG C～+100 DEG C scope measure thermal change, as glass transition temperature.
From the viewpoint of improve finished appearance and the storage period of film, in hydroxyl polymerism unsaturated monomer (k1) total amount in hydroxy acryl acid resin (K), it is preferable that containing 50 mass %～100 mass %, the polymerism unsaturated monomer (k1-1) containing secondary hydroxyl more preferably containing 80 mass %～100 mass %.
It addition, from the viewpoint of curable and finished appearance, the hydroxyl value of hydroxy acryl acid resin (K) is 140mgKOH/g～210mgKOH/g, it is preferable that in the scope of 160mgKOH/g～200mgKOH/g.
Mixing ratio for hydroxyl polymerism unsaturated monomer (k1) and other polymerism unsaturated monomer (k2), from the viewpoint of the finished appearance of curable and cured coating film, relative to total monomer amount, hydroxyl polymerism unsaturated monomer (k1) is preferably 20 mass %～50 about mass %, more preferably 30 mass %～45 about mass %, other unsaturated monomer (k2) is preferably 50 mass %～80 about mass %, more preferably 55 mass %～70 about mass %.
From the viewpoint of improve finished appearance and the storage period of film, polymerism unsaturated monomer (k1-1) containing secondary hydroxyl preferably comprises 10 mass %～50 mass % in the monomer total amount in hydroxy acryl acid resin (K), more preferably contains 20 mass %～45 mass %.
It addition, from the viewpoint of the curable of coating composition, the acid number of hydroxy acryl acid resin (K) is preferably about 0.5mgKOH/g～30mgKOH/g, it is particularly preferred to for about 1mgKOH/g～20mgKOH/g.
The monomer mixture copolymerization being made up of above-mentioned polymerism unsaturated monomer (k1) and (k2) can be obtained hydroxy acryl acid resin (K).
With the resin solid content quality total amount in clear dope (Z) for benchmark, in the hydroxy acryl acid resin (K) scope preferably in 30 mass %～70 mass %, in the scope more preferably in 35 mass %～65 mass %.
Copolymerization process for above-mentioned monomer mixture copolymerization obtains hydroxy acryl acid resin (K) is not particularly limited, copolymerization process known per se can be used, wherein, the solution polymerization process carrying out being polymerized in organic solvent under the existence of polymerization initiator can be adapted for use with.
The organic solvent used during as above-mentioned solution polymerization process, for instance can enumerate: the aromatic series kind solvents such as toluene, dimethylbenzene, Swasol1000 (Cosmo oil company manufactures, trade name, high point petroleum series solvent)；The esters solvents such as ethyl acetate, butyl acetate, acetic acid-3-methoxybutyl, ethyl cellosolve acetate, propylene glycol methyl ether acetate；The ketones solvents such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl amyl ketone；Propyl propionate, butyl propionate, ethoxyethyl propionate etc..
These organic solvents can singly use a kind or combination uses two or more, but deliquescent from the viewpoint of acrylic resin, it is preferred to use high boiling esters solvent, ketones solvent.Alternatively, it is also possible to combine the high boiling aromatic series kind solvent of use with being further adapted for.
As the polymerization initiator that can use when the copolymerization of hydroxy acryl acid resin (K), such as can enumerate: 2,2 '-azobis isobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, two t-amyl peroxy compounds, the Peroxycaprylic acid tert-butyl ester, 2, the radical polymerization initiator known per se such as 2 '-azo double; two (2-methylbutyronitrile).
Hydroxy acryl acid resin (K) can be used alone or use two or more simultaneously.
The clear dope (Z) used in the present invention can also use the resin beyond hydroxy acryl acid resin (K) optionally together.Specifically, for instance can enumerate: acrylic resin beyond hydroxy acryl acid resin (K), polyester resin, polyether resin, polyurethane resin, polycarbonate resin etc..Wherein, particularly from the viewpoint of the chipping resistance of the film obtained, tack, retouching, weatherability and ethanol petrol resistant, as preferred resin, it is possible to enumerate: hydroxyl group containing polyester resin (L1), hydroxyl polycarbonate resin (L2) and hydroxyl polycarbonate polyester resin (L3).
Hydroxyl group containing polyester resin (L1)
Hydroxyl group containing polyester resin (L1) can by conventional method, such as manufacture by the esterification of polyprotic acid and polyhydric alcohol.nullThis polyprotic acid is the compound in 1 molecule with more than 2 carboxyls，Such as can enumerate: phthalic acid、M-phthalic acid、P-phthalic acid、Succinic acid、Adipic acid、Azelaic Acid、Decanedioic acid、Tetrahydrophthalic acid、Hexahydrophthalic acid、Maleic acid、Fumaric acid、Itaconic acid、Trimellitic acid、Pyromellitic Acid and their anhydride etc.，Additionally，This polyhydric alcohol is the compound in 1 molecule with more than 2 hydroxyls，Such as can enumerate: ethylene glycol、Propylene glycol、1,Ammediol、1,4-butanediol、1,5-pentanediol、1,6-hexanediol、2,2-diethyl-1,Ammediol、Neopentyl glycol、1,9-nonanediol、1,4-cyclohexanediol、3-hydroxypivalic acid DOPCP、2-butyl-2-ethyl-1,Ammediol、3-methyl isophthalic acid,5-pentanediol、2,2,4-TMPD、Hydrogenated bisphenol A etc. and glycols；The polyol component more than ternarys such as trimethylolpropane, trimethylolethane, glycerol, tetramethylolmethane；And the hydroxy carboxylic acid etc. such as 2,2-dihydromethyl propionic acid, 2,2-dimethylolpropionic acid, 2,2-dihydroxymethyl valeric acid, 2,2-dihydroxymethyl caproic acid, 2,2-dihydroxymethyl be sad.
Additionally, (JapanEpoxyResin company manufactures can to make the alpha-olefin epoxide such as expoxy propane and epoxy butane, " CarduraE10 ", trade name, the ethylene oxidic ester of synthesis highly-branched satisfied fatty acid) etc. mono-epoxy compounds and acid reaction and these compounds are directed in polyester resin.
When importing carboxyl to polyester resin, for instance can also by carrying out half-esterification importing to hydroxyl polyester interpolation anhydride.
From the viewpoint of the chipping resistance of the film obtained, tack, retouching, weatherability and ethanol petrol resistant, hydroxyl group containing polyester resin (L1) is preferably straight-chain.From this side considerations, as above-mentioned polyprotic acid, it is preferable that adipic acid, as above-mentioned polyhydric alcohol, it is preferable that ethylene glycol, propylene glycol, 1,3-PD, BDO, 1,5-PD, 1,6-hexanediol.
The hydroxyl value of hydroxyl group containing polyester resin (L1) is preferably in the scope of 85～250mgKOH/g, it is preferred that in the scope of 100～220mgKOH/g.The number-average molecular weight of hydroxyl group containing polyester resin (L1) is preferably in the scope of 500～2500, it is preferred that in the scope of 800～2000.
Hydroxyl polycarbonate resin (L2)
Hydroxyl polycarbonate resin (L2) is the polycarbonate resin being respectively provided with more than 2 carbonate groups and hydroxyl in molecule.
Hydroxyl polycarbonate resin (L2) is the compound that can obtain by making known polyhydric alcohol and carbonyl agent carry out polycondensation reaction according to conventional method.
Polyhydric alcohol as the raw material becoming hydroxyl polycarbonate resin (L2), it is possible to enumerate: the alcohol of glycol and more than 3 yuan.
In becoming the polyhydric alcohol of raw material of hydroxyl polycarbonate resin (L2), as glycol, can enumerate: 1,3-PD, BDO, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptandiol, 1,8-ethohexadiol, 1, the branched aliphatic category glycol such as 9-nonanediol and decamethylene-glycol；2-methyl isophthalic acid, 3-propane diol, 3-methyl isophthalic acid, 5-pentanediol, neopentyl glycol, 2-ethyl-1,6-HD, 2,2-diethyl-1, ammediol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl isophthalic acid, 8-ethohexadiol, 2,2, the branched aliphatic category glycol such as 4-trimethyl-1,3-pentanediol, 2-ethyl 1,3-hexanediol；The ester ring type class glycol such as 1,3-cyclohexane diol, 1,4-cyclohexane diol, 1,4 cyclohexane dimethanol；Xylol glycol, to the fragrance such as tetrachloro Xylene glycol same clan glycol；The ethers glycol such as diethylene glycol, dipropylene glycol etc..These glycol can be used alone or combine and use two or more.
In becoming the polyhydric alcohol of raw material of hydroxyl polycarbonate resin (L2), as alcohol more than ternary, it is possible to enumerate: glycerol, trimethylolethane, trimethylolpropane, the dimer of trimethylolpropane, tetramethylolmethane etc..Alcohol more than these ternarys can be used alone or combines and uses two or more.
As the carbonyl agent of the raw material becoming hydroxyl polycarbonate resin (L2), known carbonyl agent can be used.Specifically, for instance can enumerate: alkylene carbonates, dialkyl carbonate, diaryl carbonate, phosgene etc., can use they a kind or combination use two or more.As wherein preferred carbonyl agent, it is possible to enumerate: ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, diphenyl carbonate etc..
From the viewpoint of chipping resistance, tack, retouching, weatherability and ethanol petrol resistant, hydroxyl polycarbonate resin (L2) preferably comprises the hydroxyl polycarbonate resin (following, to be sometimes referred to as " PCDL (L2-1) ") that hydroxyl is 2.
Above-mentioned PCDL (L2-1) can not use the polyhydric alcohol such as the alcohol of more than 3 yuan and only by using glycol to synthesize as the polyhydric alcohol reacted with above-mentioned carbonyl agent.
As the diol component of PCDL (L2-1), carbon number more than 6, preferred carbon number 6～20, more preferably carbon number 6～15 generally can be used it is preferred that the glycol of carbon number 6～12.
Glycol as carbon number more than 6, it is possible to enumerate: the aliphatic category glycol of the alicyclic ring same clan glycol with the ring alkylidene of carbon number more than 6 and the alkylidene with carbon number more than 6.
Alicyclic ring same clan glycol as the ring alkylidene with carbon number more than 6, can enumerate: 1,3-cyclohexanediol, Isosorbide-5-Nitrae-cyclohexanediol, 1,4-CHDM etc. are as the alicyclic diol of the carbon number more than 6 of glycol entirety, preferred carbon number 6～12.
In above-mentioned, from the viewpoint of chipping resistance, it is preferable that 1,4-CHDM.
Aliphatic category glycol as the alkylidene with carbon number more than 6, it is possible to enumerate: the straight-chain aliphatic category glycol such as 1,6-hexanediol, 1,7-heptandiol, 1,8-ethohexadiol, 1,9-nonanediol and decamethylene-glycol；3-methyl isophthalic acid, 5-pentanediol, 2-ethyl-1,6-hexanediol, 2,2-diethyl-1,3-propylene glycol, 2-butyl-2-ethyl-1, ammediol, 2-methyl isophthalic acid, 8-ethohexadiol, 2,2,4-trimethyl-1, the aliphatic category glycol of the carbon numbers more than 6 such as branched aliphatic category glycol such as 3-pentanediol, 2-ethyl-1,3-hexanediol, the straight-chain of preferred carbon number 6～10 or branched.
The aliphatic category glycol of above-mentioned straight-chain aliphatic category glycol and branched can use the one in them, it is also possible to combination uses both.
In above-mentioned, from the viewpoint of chipping resistance, it is preferable that straight-chain aliphatic category glycol, it is particularly preferred to 1,6-hexanediol.
Considering from viewpoints such as the resistances to impact chipping resistance, low temperature, the number-average molecular weight of above-mentioned hydroxyl polycarbonate resin (L2) is preferably 500～2500, more preferably 800～2000.
Market sale product as (L2), it is possible to enumerate: UM-90, UH-100, UH-200, UC-100 (trade name, Yu Buxingchan company manufactures) etc..
Hydroxyl polycarbonate polyester resin (L3)
From the viewpoint of the resistance to impact under low temperature, more preferably use hydroxyl polycarbonate polyester resin (L3).
Hydroxyl polycarbonate polyester resin (L3) such as can pass through to utilize known method to make above-mentioned polycarbonate polyester (L2) react with cyclic ester compounds and manufacture.
As cyclic ester compounds, for instance can enumerate: δ-valerolactone, 6-caprolactone, ζ-heptalactone, η-caprylolactone, gamma-valerolactone, δ-caprolactone, ε-heptalactone, ξ-caprylolactone, Beta-methyl-gamma-valerolactone, it is particularly preferred to for 6-caprolactone.
Considering from viewpoints such as the resistances to impact chipping resistance, low temperature, the number-average molecular weight of above-mentioned hydroxyl polycarbonate polyester resin (L3) is preferably 500～2500, more preferably 800～2000.
The total amount of hydroxyl group containing polyester resin (L1), hydroxyl polycarbonate resin (L2) and hydroxyl polycarbonate polyester resin (L3) preferably with respect to the solid constituent total amount of hydroxy acryl acid resin (K) in below 100 mass %, the scope more preferably in 10 mass %～50 mass %.
Above-mentioned cross-linking agent as clear dope, can enumerate: having can with the melmac of reactive functional groups of the above-mentioned functional group reactions of matrix resin, urea resin, (end-blocking) polyisocyanate compounds, epoxide, carboxylated compound, anhydride, compound etc. containing alkoxysilane group, it is particularly preferred to polyisocyanate compounds (PI).
Polyisocyanate compounds (PI)
Polyisocyanate compounds (PI) is the compound in 1 molecule with more than 2 NCOs.As polyisocyanate compounds (PI), it is possible to enumerate: as the derivant etc. of polyurethane manufacture known compound, such as aliphatic polymeric isocyanate, alicyclic polymeric isocyanate, aromatic-aliphatic polyisocyanate, aromatic poly-isocyanate and these polyisocyanate.
As aliphatic polymeric isocyanate, specifically, such as can enumerate: trimethylene diisocyanate, tetramethylene-1,4-diisocyanate, pentamethylene-1,5-diisocyanate, hexamethylene diisocyanate, 1,2-trimethylene diisocyanate, 1,2-tetramethylene diisocyanate, 2,3-tetramethylene diisocyanate, 1,3-tetramethylene diisocyanate, 2,2,4-trimethyls-hexa-methylene-1, the aliphatic diisocyanates such as 6-diisocyanate, 2,6-bis-isocyanato-methyl caproates, lysinediisocyanate；Lysine ester triisocyanate, 1,4,8-tri-isocyanato-octane, 1,6,11-tri-isocyanato-hendecane, 1,8-bis-isocyanato--4-isocyanatomethyl octane, 1,3,6-tri-isocyanato-hexane, 2,5, the aliphatic triisocyanates etc. such as 7-trimethyl-1,8-two isocyanato--5-isocyanatomethyl octane.
nullAs above-mentioned alicyclic polymeric isocyanate，Such as can enumerate: 1,3-cyclopentene diisocyanate、1,4-cyclohexane diisocyanate、1,3-cyclohexane diisocyanate、3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (trivial name: isophorone diisocyanate)、4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate)、Methyl-2,4-cyclohexane diisocyanate、Methyl-2,6-cyclohexane diisocyanate、1,3-or 1,Double; two (isocyanatomethyl) hexamethylene (trivial name: hydrogenated xylylene diisocyanate) of 4-or its mixture、The alicyclic diisocyanates such as norbornene alkyl diisocyanate、Such as 1,3,5-tri-isocyanatocyclohexane、1,3,5-trimethyl isocyanatocyclohexane、2-(3-isocyanatopropyl)-2,5-bis-(isocyanatomethyl)-dicyclo (2.2.1) heptane、2-(3-isocyanatopropyl)-2,6-bis-(isocyanatomethyl)-dicyclo (2.2.1) heptane、3-(3-isocyanatopropyl)-2,5-bis-(isocyanatomethyl)-dicyclo (2.2.1) heptane、5-(2-isocyanatoethyl)-2-isocyanatomethyl-3-(3-isocyanatopropyl)-dicyclo (2.2.1) heptane、6-(2-isocyanatoethyl)-2-isocyanatomethyl-3-(3-isocyanatopropyl)-dicyclo (2.2.1) heptane、5-(2-isocyanatoethyl)-2-isocyanatomethyl-2-(3-isocyanatopropyl)-dicyclo (2.2.1)-heptane、The alicyclic triisocyanates etc. such as 6-(2-isocyanatoethyl)-2-isocyanatomethyl-2-(3-isocyanatopropyl)-dicyclo (2.2.1) heptane.
As aromatic-aliphatic polyisocyanate, such as can enumerate: 1,3-or 1,4-XDI or its mixture, ω, ω '-two isocyanato--Isosorbide-5-Nitrae-diethylbenzene, 1,3-or 1, the aromatic-aliphatic triisocyanates etc. such as 4-double; two (1-isocyanato--1-Methylethyl) araliphatic diisocyanate such as benzene (trivial name: tetramethylxylene diisocyanate) or its mixture, such as 1,3,5-tri-isocyanatomethylbenzene.
As aromatic poly-isocyanate, such as can enumerate: metaphenylene diisocyanate, to phenylene vulcabond, 4, 4 '-diphenyl diisocyanate, 1, 5-naphthalene diisocyanate, 2, 4 '-or 4, 4 '-methyl diphenylene diisocyanate or its mixture, 2, 4-or 2, 6-toluene di-isocyanate(TDI) or its mixture, 4, 4 '-toluidine diisocyanate, 4, the aromatic diisocyanates such as 4 '-diphenyl ether diisocyanate, such as triphenyl methane-4, 4 ', 4 " '-triisocyanate, 1, 3, 5-tri-isocyanato-benzene, 2, 4, the aromatic tri-isocyanates such as 6-tri-isocyanato-toluene, such as 4, 4 '-diphenyl methane-2, 2 ', 5, the aromatic series tetraisocyanates etc. such as 5 '-tetraisocyanate.
Additionally, derivant as polyisocyanate, for instance can enumerate: the dimer of above-mentioned polyisocyanate compounds, trimer, biuret, allophanate, adduct, carbodiimide, urea diketone, urea imines, isocyanuric acid ester, diazine triketone, polymethylene polyphenyl base polyisocyanate (thick MDI, polymeric MDI) and thick TDI etc..
In above-mentioned, the easiness obtained from industry considers, can be particularly suitable for using hexamethylene diisocyanate (hereinafter sometimes referred to HMDI), isophorone diisocyanate (hereinafter sometimes referred to IPDI) and their derivant.
Above-mentioned polyisocyanate compounds can be used alone or use two or more simultaneously.
The content of polyisocyanate compounds (PI) preferably with respect to the solid constituent total amount of hydroxy acryl acid resin (K) in below 200 mass %, the scope more preferably in 50 mass %～150 mass %.
Curing catalysts as clear dope, can individually use or combine two or more known curing catalysts of use, such as tin octoate, dibutyl tin acetate, dibutyl two (2 ethyl hexanoic acid) stannum, dibutyl tin dilaurate, dioctyl oxalic acid stannum, dioctyl two (2 ethyl hexanoic acid) stannum, Dibutyltin oxide, dioctyl tin oxide, dibutyl tin soap, dibutyl tin bis-fatty acid salt, 2 ethyl hexanoic acid is plumbous, zinc octoate, zinc naphthenate, fatty acid zinc class, cobalt naphthenate, calcium octoate, copper naphthenate, the organo-metallic compounds such as four (2-ethylhexyl) titanate esters；Tertiary amine etc..
Wherein, it is preferable that organo-metallic catalyst (M).Organo-metallic catalyst (M) is the catalyst being made up of zinc compound (M-I) and amidine compound (M-II).By using zinc compound (M-I) and amidine compound (M-II) simultaneously so that the curable in low-temperature short-time is excellent, and the finished appearance of the film formed is good, and can be maintained to a certain degree the storage period as 2 liquid type coating.
It is thought that the catalyst because being made up of zinc compound (M-I) and amidine compound (M-II) forms complex structure, amidine compound becomes end-capping reagent, amidine compound as this end-capping reagent dissociates at low temperatures, after amidine compound dissociation, the catalytic performance activation that zinc compound curability at low temperatures originally is excellent, thus, the curable in the low-temperature short-time of coating composition can be had both and storage period can be maintained to a certain degree.
As zinc compound (M-I), for instance can enumerate: salts of carboxylic acids compound, acetylacetone,2,4-pentanedione zinc complex etc..Especially, can be suitable for using salts of carboxylic acids compound.
As salts of carboxylic acids compound, specifically, it is possible to enumerate the compound shown in following formula (1).
(RCO2)nZn(1)
(in formula, R represents the alkyl of carbon number 1～30, the aralkyl of carbon number 1～30 or alkylaryl, and n is the integer with more than 1 and 4 value below)
More specifically, for instance can enumerate: 2 ethyl hexanoic acid zinc, zinc acetate, zinc octoate, zinc naphthenate, zinc octoate, zinc stearate, zinc neodecanoate, zinc oleate etc..
From the viewpoint of catalysis superior activity and industrial obtain easy, can be particularly suitable for use zinc octoate.
Amidine compound (M-II) has R1-C (=NR2)-NR3R4The organic compound of shown structure.In the structure shown here, there is 1 nitrogen-atoms and be bonded to carbon (C) atom and 1 nitrogen-atoms with singly bound in the structure of carbon (C) atom with double bond.
In formula R1-C (=NR2)-NR3R4(1) in,
R1It is hydrogen atom, commutable is bonded to the organic group of carbon atom, amino, specifically, it is possible to enumerate: commutable alkyl or can the hydroxyl of etherificate.
R2And R3Mutually independent, it is hydrogen atom or the organic group being bonded to carbon atom or the heterocycle with the structure of bonding mutually (comprise the hetero atom with more than 1 or 2 or there is the dicyclo of heteroatomic bonding of more than 1 or 2).
R4Can enumerate: hydrogen atom, commutable be bonded to carbon atom organic group, can the hydroxyl of etherificate, it may be preferable to enumerate: the alkyl of commutable carbon number more than 8.
At R1Or R4When being organic group, they can be the group of the carbon atom such as with 1 to 40 or such as have 500～50000 the polymeric groups of molecular weight.
R1、R2、R3、R4Shown group can contain alcohol hydroxyl group alternatively base independently of one another.
As by formula R1-C (=NR2)-NR3R4(1) expression and R2With R3The amidine compound not being bonded, specifically, it is possible to enumerate:
N '-cyclohexyl-N, N-dimethyl carbonamidine, N '-methyl-N, N-di-n-butyl ethanamidine, N '-octadecyl-N, N-dimethyl carbonamidine, N '-cyclohexyl-N, N-dimethyl-penten amidine, 1-methyl-2-cyclohexylimino pyrrolidine, 3-butyl-3,4,5,6-tetrahydropyrimidine, N-(hexyl iminomethyl) morpholine, N-(α-(decyl Iminoethyl) ethyl) pyrrolidine, N '-decyl-N, N-dimethyl carbonamidine, N '-decyl-N, N-dimethyl carbonamidine, N '-cyclohexyl-N, N-ethanamidine etc..
It addition, as this amidine compound, there is R2-R3Comprise 5 to 7 rings of 2 nitrogen-atoms in amidine structure and R1-R3Or R1-R4In the amidine compound of 1 structure forming 5 to 9 rings by 1 nitrogen-atoms in amidine structure and multiple carbon atom be also contained in amidine compound (M-II).
As the amidine compound having a structure in which, specifically, can enumerate: 1,5-diazabicyclo (4.3.0) ketone-5-alkene, 1,8-diazabicyclo (5.4.0) 11 carbon-7-alkene, 1, pungent-4-the alkene of 4-diazabicyclo (3.3.0), 2-methyl isophthalic acid, 5-diazabicyclo (4.3.0) ketone-5-alkene, 2,7,8-trimethyl-1,5-diazabicyclo (4.3.0) ketone-5-alkene, 2-butyl-1,5-diazabicyclo (4.3.0) ketone-5-alkene, 1,9-diazabicyclo (6.5.0) 13 carbon-8-alkene etc..
It addition, as amidine compound, it is possible to enumerate: there is formula R1-C (=NR2)-NR3R4(1) R in2With R3The heterocyclic compound of structure of bonding, such as imidazoline, imidazoles, tetrahydropyrimidine, dihydro-pyrimidin, pyrimidine.
Imdazole derivatives is generally represented by following structural formula.
[chemical formula 14]
In above-mentioned, as R5、R6、R7And R8, each independent mutually, can enumerate: hydrogen atom, alkyl or replacement alkyl, hydroxy alkyl, pi-allyl, aralkyl, cycloalkyl, heterocycle, ether, thioether, halogen ,-N (R)2, polyethylene polyamines, nitro, ketone group, ester group, carbon acylamino and these functional groups alkyl substituent.
nullAs imidazolium compounds，Specifically，Can enumerate: N-(2-ethoxy) imidazoles、N-(3-aminopropyl) imidazoles、4-(methylol) imidazoles、1-(tert-butoxycarbonyl) imidazoles、Imidazoles-4-propanoic acid、4-carboxyl imidazoles、1-1-Butyl-1H-imidazole、1-Methylimidazole.、2-methyl-4-imidazolyl carboxylic acid、4-formyl imidazoles、1-(ethoxy carbonyl) imidazoles、The reactant of expoxy propane and imidazoles and 2-methylimidazole、1-trimethyl-silyl-imidazole、4-(methylol) imidazole hydrochloride、1-chloro-2,The copolymer of 3-expoxy propane and imidazoles、1-(p-toluenesulfonyl) imidazoles、1,1-carbonyldiimidazole、1-(2-cyano ethyl)-2-ethyl-4-methylimidazole、2-phenyl-2-imidazoline pyromellitic ester、4-(methylol) imidazoles picrate、2-acrylic acid and 4,5-dihydro-2-nonyl-1H-imidazoles-1-ethanol and 2-heptyl-4,The disodium salt of 5-dihydro-1H-imidazoles-1-ethanol、1-(cyano ethyl)-2-undecyl imidazole trimellitate、The formic acid esters of 1-(2-hydroxypropyl) imidazoles、Imidazole natrium、Imidazoles silver etc..
Above-mentioned amidine compound can be used alone or use two or more simultaneously.
Specifically, in the present invention, organo-metallic catalyst (M) is zinc complex, and this complex such as can by being heated manufacturing in methanol equal solvent by the zinc polycarboxylate of 1 mole and the amidine compound of 2 moles.
In above-mentioned manufacture, make zinc complex until becoming transparent solution state by keeping at about 50 DEG C about 2 hours.Filter this clear solution and dry.
The mol ratio (value of the molal quantity of the molal quantity of (M-II)/(M-I)) of amidine compound (M-II) and zinc compound (M-I) is preferably the scope of 1.3～8.0, it is particularly preferably the scope of 1.6～5.0, is particularly preferably the scope of 1.8～4.0 further.
If above-mentioned mol ratio is outside the scope of 1.3～8.0, then between low-temperature short-time, curable, storage period and finished appearance all become insufficient sometimes.
From the viewpoint of curable, storage period and finished appearance between low-temperature short-time, relative to (K) composition, at least one in (L1) composition, (L2) composition and (L3) composition, (PI) composition total amount, (M) in the amount of the composition scope preferably in 0.05 mass %～5 mass %, in scope particularly preferably in 0.1 mass %～4 mass %, further particularly preferably in the scope of 0.3 mass %～3 mass %.If less than 0.05 mass %, then between low-temperature short-time, curable becomes insufficient sometimes.It addition, if it exceeds 5 mass %, then the finished appearance of the film sometimes obtained becomes insufficient.
Organo-metallic catalyst (M) is also dissolvable in water solvent and uses.Solvent is not particularly limited, for instance can enumerate: the gylcol ethers such as the ketones such as esters, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), Ketohexamethylene such as the hydro carbons such as the alcohols such as ethylene glycol, diethylene glycol, dipropylene glycol, propylene glycol, butanediol, toluene, dimethylbenzene, mineral turpentine, mineral spirits, ethyl acetate, butyl acetate, ethylene glycol methyl acetate, cellosolve acetate, 3-ethoxyl ethyl propionate, 3-2-Methoxyacetic acid butyl ester；The organic solvent equal solvent of the amide-type such as N,N-dimethylformamide, DMAC N,N' dimethyl acetamide.
In the coating composition of the present invention, as catalyst, except organo-metallic catalyst (M), it is also possible to use the catalyst beyond organo-metallic catalyst (M) as required.
It is not particularly limited as the catalyst beyond above-mentioned organo-metallic catalyst (M), as long as the existing known organic metal as polyurethane catalyst for producing, specifically, it is possible to enumerate: the organotin catalysts such as oxalic acid stannum, two tin octoates, two oleic acid stannum, tin dilaurate stannum, Dibutyltin oxide, dibutyltin diacetate, dibutyl tin laurate, dibutyl tin dichloride, tin dilaurate dioctyl tin.Wherein, it is preferable that two tin octoates, dibutyl tin laurate.
End-capping reagent (N)
The end-capping reagent (N) used in clear dope is chosen from beta-diketon class, beta-keto acid esters, malonic acid esters, β position have the ketone of hydroxyl, β position has the aldehydes of hydroxyl and β position has the compound of at least one in the esters of hydroxyl.
Specifically, for instance can enumerate: beta-diketon class: acetylacetone,2,4-pentanedione, benzoyl, dibenzoyl methane, beta-keto acid esters: ethyl methyl ester, ethyl acetoacetate, ethyl benzoylacetate, malonic acid esters: malonic ester, β position have the ketone of hydroxyl: DAA, β position have the aldehydes of hydroxyl: salicylide, β position have the esters of hydroxyl: methyl salicylate etc..
In above-mentioned, particularly high from the viewpoint of extended pot life effect, it is preferable that beta-diketon class, it is particularly preferred to acetylacetone,2,4-pentanedione.
Relative to K) composition, at least one in (L1) composition, (L2) composition and (L3) composition, (PI) composition solid constituent total amount, the amount of end-capping reagent (N) is 0.7 mass %～25 mass %, it is preferably 1.0 mass %～20 mass %, more preferably 2.0 mass %～15 mass %.
The amount of end-capping reagent (N) is relative to K) composition, at least one in (L1) composition, (L2) composition and (L3) composition, (PI) if the solid constituent total amount of composition is lower than 0.7 mass %, then extended pot life effect becomes insufficient sometimes, if it exceeds 25 mass %, then extended pot life effect culminates, additionally, the curable of the film sometimes obtained becomes insufficient.
As above-mentioned UV absorbent, existing known UV absorbent can be used, for instance can enumerate: the UV absorbent such as benzotriazole system absorbent, triazine system absorbent, salicyclic acid derivatives system absorbent, benzophenone series absorbent.
As the content in the clear dope (Z) of UV absorbent, from the viewpoint of weather resisteant, yellowing resistance, it is commonly angled relative to resin solid content total amount, in scope preferably in 0 mass %～10 mass %, in scope particularly preferably in 0.2 mass %～5 mass %, further particularly preferably in the scope of 0.3 mass %～2 mass %.
As above-mentioned light stabilizer, existing known light stabilizer can be used, for instance can enumerate: hindered amine light stabilizer.
As the content in the clear dope (Z) of light stabilizer, from the viewpoint of weather resisteant, yellowing resistance, it is commonly angled relative to resin solid content total amount, it is preferably 0 mass %～10 mass %, it is particularly preferably 0.2 mass %～5 mass %, further particularly preferably in the scope of 0.3 mass %～2 mass %.
In one embodiment, clear dope (Z) is containing the hydroxy acryl acid resin (K) being benchmark 30 mass %～70 mass % with the resin solid content quality total amount of clear dope, relative to the solid constituent total amount of hydroxy acryl acid resin (K) be below 100 mass % selected from hydroxyl group containing polyester resin (L1), at least one resin in hydroxyl polycarbonate resin (L2) and hydroxyl polycarbonate polyester resin (L3) and be preferably the polyisocyanate compounds (PI) of below 200 mass % relative to the solid constituent total amount of hydroxy acryl acid resin (K).
In another embodiment, clear dope (Z) is containing the hydroxy acryl acid resin (K) being benchmark 30 mass %～70 mass % with the resin solid content quality total amount of clear dope；Relative at least one resin in hydroxyl group containing polyester resin (L1), hydroxyl polycarbonate resin (L2) and hydroxyl polycarbonate polyester resin (L3) that the solid constituent total amount of hydroxy acryl acid resin (K) is below 100 mass %；The polyisocyanate compounds (PI) of below 200 mass % it is preferably relative to the solid constituent total amount of hydroxy acryl acid resin (K)；The organo-metallic catalyst (M) that total amount is 0.05 mass %～5 mass % relative to (K) composition, at least one being selected from (L1) composition, (L2) composition and (L3) composition and (PI) composition；With the end-capping reagent (N) that solid constituent total amount is 0.7 mass %～25 mass % relative to (K) composition, at least one being selected from (L1) composition, (L2) composition and (L3) composition and (PI) composition.
The clear dope (Z) used in the present invention can be a liquid type coating, it is also possible to be the mulit liquid type coating such as two-liquid type coating.In this clear dope (Z), when using polyisocyanate compounds (PI) as above-mentioned cross-linking agent, from the viewpoint of storage stability, it is preferably formed the two-liquid type coating being made up of the host containing above-mentioned matrix resin and the cross-linking agent containing above-mentioned polyisocyanate compounds (PI), before the use both is mixed use.
Coating process as clear dope (Z) is not particularly limited, for instance can pass through the coating process such as aerial spraying application, airless spraying application, rotary-atomizing application, curtain painting application and form wet coating.In these coating process, it is also possible to optionally apply electrostatic.Wherein, it is particularly preferred to aerial spraying application.The thickness of clear dope (Z) is generally preferable is calculated as 10～50 μm solidifying thickness, it is preferred to 20～45 μm.
Additionally, when carrying out aerial spraying application, airless spraying application and rotary-atomizing application, it is preferable that use organic solvent equal solvent to be suitable for adjusting the viscosity of clear dope (Z) in advance so that it is the range of viscosities of about 15～60 seconds that the range of viscosities that is suitable to this application is that typically in Ford cup #No.4 viscometer at 20 DEG C.
Operation (4)
The multilayer film being made up of the 1st painted film formed as discussed above, the 2nd painted film and this 3 coating film of transparent coating can be heated by the sintering method of common film, such as Hot-blast Heating, infrared heating, high-frequency heating etc..
The aspect that curable from low temperature is excellent considers, heating keeps temperature (maintenance temperature) to be adapted in the scope of 60 DEG C～140 DEG C, is particularly suitable in the scope of 70 DEG C～120 DEG C.Heated hold time (retention time) is adapted in the scope of 10 minutes～50 minutes, is particularly suitable in the scope of 20 minutes～40 minutes.
Before carrying out above-mentioned sintering curing, optionally at room temperature sizing 1 minute～about 60 minutes and/or carry out the preheating of about 1～60 minute at the temperature of 40～80 DEG C.
The method of forming layered coating film of the present invention can form the film being respectively provided with the chipping resistance of excellence, tack, retouching, weatherability and ethanol petrol resistant relative to metal parts or plastic components.
The present invention can be suitable as the method for forming layered coating film containing metal material and whole industrial products of plastic material.Wherein, the method for forming layered coating film of automobile can be especially suitable for use as.
By the method for forming layered coating film of the present invention, the reason that can form the film being respectively provided with the chipping resistance of excellence, tack, retouching, weatherability and ethanol petrol resistant relative to metal parts or plastic components is not yet determined, but can speculate as follows.In the method for forming layered coating film of the present invention, aqueous the 1st pigmented finiss contains specific waterborne polyurethane resin, and therefore, opposing metallic parts or plastic components are respectively provided with the tack of excellence.Thus, thus it is speculated that the chipping resistance of display excellence and ethanol petrol resistant.It addition, aqueous the 1st pigmented finiss contains blocked polyisocyanate, therefore, low temperature and the curable in the short time are excellent.It addition, by the curable of this excellence, the crosslink density of film uprises, therefore, resistance to water, tack are excellent.And then, by the curable of this excellence, bring the viscosity of the 1st painted film to manifest effect, the mixed layer with the 2nd painted film during application can be suppressed, the reduction of finished appearance because of the multilayer film caused by mixed layer can be suppressed.It addition, the light transmittance of the multilayer film that supposition is owing to obtaining further is low, thus can suppress because of the deterioration of photogenic film, therefore, the film with the chipping resistance of excellence, tack, wettability, weatherability and ethanol petrol resistant can be formed.
Think by these synergies, by the method for forming layered coating film of the present invention, the film being respectively provided with the chipping resistance of excellence, tack, retouching, weatherability and ethanol petrol resistant relative to metal parts or plastic components can be formed.And then, in the multilayer film formed by the method for forming layered coating film of the present invention, the storage period of clear dope can maintain suitable length.
Embodiment
Hereinafter, enumerate embodiment and comparative example specifically describes the present invention further.But, the present invention is not limited in these embodiments.It addition, " part " and " % " is all according to quality criteria.It addition, the thickness of film is based on cured coating film.
The manufacture of aqueous the 1st pigmented finiss (X)
The manufacture of chlorine-free polyolefin-based resins (A)
Manufacture example 1
The mixture being made up of the maleation polypropylene resin (chlorination rate 22%, maleic acid modified amount 2.0%, acid number 30mgKOH/g) 500 parts of weight average molecular weight 80000, normal heptane 150 parts and N-Methyl pyrrolidone 50 parts is heated to 50 DEG C, add dimethylethanolamine 12 parts and " NOIGENEA-140 " (nonionic class surfactant, 1st industrial pharmaceutical (strain) manufactures, trade name) 5 parts, after synthermal lower stirring 1 hour, it is slowly added to deionized water 2000 parts, carries out stirring in 1 hour further.
Then, reduce pressure at the temperature of 70 DEG C, be distilled off adding up to 600 parts of normal heptane and water, obtain chlorine-free vistanex dispersion liquid (A-1) of solid constituent containing ratio 23.6%.
Manufacture example 2
In the four-hole boiling flask being provided with agitator, condensing tube, thermometer and Dropping funnel, by maleic anhydride inoculated polypropylene (relative to the polypropylene using Metallocene-type catalysts to obtain, the material being modified with maleic acid addition amount 4 mass % and obtain, fusing point 80 DEG C, Mw about 150,000, Mw/Mn about 2.5) 100g adds heat fusing at 140 DEG C, add polyoxyethylene stearyl base ether (" Newcol1820 ", single end hydroxyl polyoxyethylene compound, emulsifying agent company of Japan manufactures) 15g, stirs and carries out reaction in 4 hours at 140 DEG C.After reaction, it is cooled to 90 DEG C, adds deionized water and be filtered, obtain chlorine-free vistanex dispersion liquid (A-2) of solid constituent 30%.
The manufacture of waterborne polyurethane resin (B)
Manufacture example 3
Possessing thermometer, blender, reactive tank addition polytetramethylene glycol (number-average molecular weight 1000) 211.9 parts of reflux condenser, α, α-dihydromethyl propionic acid 11.5 parts, trimethylolpropane 6.9 parts, isophorone diisocyanate 112.2 parts and methyl ethyl ketone 298.5 parts, after reaction system is replaced with nitrogen, make it react when stirring in 80 DEG C, obtain the NCO end urethane prepolymer of free isocyanate group content 3.2%.This methyl ethyl ketone solution obtained is cooled to 40 DEG C, after adding the deionized water 493.2g emulsifying containing triethylamine 5.2 parts, add 5% ethylenediamine solution 159.2 parts wherein, after stirring 60 minutes, methyl ethyl ketone is distilled off under heating under reduced pressure, carry out concentration adjustment with deionized water, obtain the waterborne polyurethane resin dispersion liquid (B-1) of 15 minutes time needed for solid constituent 35%, film forming at the temperature of 20 DEG C, acid number 14mgKOH/g, mean diameter 120nm.
Manufacture example 4～13
In manufacturing example 3, cooperation composition is set as shown in table 1, in addition, obtains each waterborne polyurethane resin dispersion liquid (B-2)～(B-11) by operation in the same manner as manufacturing example 3.
Representing it addition, the cooperation of table 1 is solids content, (note 1) in table 1 is as shown in following.
The manufacture of (note 1) PEPA A
The sodium salt 49 parts of Polyethylene Glycol (number-average molecular weight 300) 67 parts and 5-dimethyl sulfoisophthalate and Dibutyltin oxide 0.2 part are incorporated in reaction vessel, 190 DEG C it are warming up under the decompression state of 5mmHg, distillation for removing methanol is while carrying out 6 hours ester exchange reactions on one side, obtains the PEPA A on average in 1 molecule with 5 sodium sulfonate groups, hydroxyl value 29.6mgKOH/g, number-average molecular weight 3700.
[table 1]
Table 1
There is the manufacture of the blocked polyisocyanate compound (C) of nonionic hydrophilic group
Manufacture example 14
Possessing thermometer, thermostat, agitating device, reflux condenser, nitrogen ingress pipe, Dropping feeder and except the simple and easy grabber of solvent reaction vessel in add " SumiduleN-3300 " (trade name, firmly change Bayer urethane company manufactures, it is derived from the polyisocyanate containing isocyanurate structure of hexamethylene diisocyanate, solid constituent about 100%, NCO containing ratio 21.8%) 1610 parts, " UNIOXM-550 " (You company manufactures, MPEG-550, mean molecule quantity about 550) 275 parts and 2, 6-di-tert-butyl-4-methy phenol 0.9 part, it is sufficiently mixed, under nitrogen stream, (Chisso flows down In) heats 3 hours in 130 DEG C.Then, add ethyl acetate 550 parts and Diisopropyl malonate 1150 parts, under nitrogen stream, stir 28% methanol solution 14 parts adding Feldalat NM, stir 8 hours at 65 DEG C.Amount of isocyanate in the resin solution obtained is about 0.1 mole/kg.Add 4-methyl-2-amylalcohol 3110 parts wherein, the temperature of system is maintained at 80 DEG C～85 DEG C one side and solvent was distilled off through 3 hours at reduced pressure conditions, obtain blocked polyisocyanate compound solution (C-1) 4920 parts.Except the simple and easy grabber of solvent contains 585 parts of isopropanols.The solid component concentration of the blocked polyisocyanate compound solution (C-1) obtained is about 60%.
Manufacture example 15
Possessing thermometer, thermostat, agitating device, reflux condenser, nitrogen ingress pipe, Dropping feeder and except the simple and easy grabber of solvent reaction vessel in add " SumiduleN-3300 " (trade name, firmly change Bayer urethane company manufactures, it is derived from the polyisocyanate containing isocyanurate structure of hexamethylene diisocyanate, solid constituent about 100%, NCO containing ratio 21.8%) 1610 parts, " UNIOXM-550 " (You company manufactures, MPEG-550, mean molecule quantity about 550) 275 points and 2, 6-di-tert-butyl-4-methy phenol 0.9 part, it is sufficiently mixed, heat 3 hours in 130 DEG C under nitrogen stream.Then, add ethyl acetate 550 parts and Diisopropyl malonate 1150 parts, under nitrogen stream, stir 28% methanol solution 14 parts adding Feldalat NM, stir 8 hours at 65 DEG C.Amount of isocyanate in the resin solution obtained is about 0.1 mole/kg.The solid component concentration of the blocked polyisocyanate compound solution (C-2) obtained is about 60%.
Manufacture example 16
" SumiduleN-3300 " 1610 parts and hydroxy new pentane acid 236 parts is added in possessing thermometer, thermostat, agitating device, reflux condenser, nitrogen ingress pipe, Dropping feeder and the reaction vessel except the simple and easy grabber of solvent, stirring while being sufficiently mixed, heating 3 hours in 130 DEG C under nitrogen stream.Then, add ethyl acetate 550 parts and Diisopropyl malonate 930 parts, under nitrogen stream, stir 28% methanol solution 14 parts adding Feldalat NM, stir 8 hours at 65 DEG C.Amount of isocyanate in the resin solution obtained is about 0.1 mole/kg.Add 4-methyl-2-amylalcohol 2530 parts wherein, the temperature of system is maintained at 80 DEG C～85 DEG C one side and solvent was distilled off through 3 hours at reduced pressure conditions, obtain blocked polyisocyanate compound solution (C-3) 4450 parts.Except the simple and easy grabber of solvent contains 475 parts of isopropanols.The solid component concentration of the blocked polyisocyanate compound solution (C-3) obtained is about 60%.
Manufacture example 17
Possessing thermometer, thermostat, agitating device, reflux condenser, nitrogen ingress pipe, Dropping feeder and except the simple and easy grabber of solvent reaction vessel in add " SumiduleN-3300 " (trade name, firmly change Bayer urethane company manufactures, it is derived from the polyisocyanate containing isocyanurate structure of hexamethylene diisocyanate, solid constituent about 100%, NCO containing ratio 21.8%) 480 parts, ethyl acetate 150 parts and Diisopropyl malonate 365 parts, stir while adding 28% methanol solution 4 parts of Feldalat NM under nitrogen stream, stir 8 hours at 65 DEG C.Amount of isocyanate in the resin solution obtained is 0.07 mole/kg.Add 4-methyl-2-amylalcohol 870 parts wherein, while the temperature of system being maintained at 80 DEG C～85 DEG C solvent was distilled off through 3 hours at reduced pressure conditions, add 4-methyl-2-amylalcohol 120 parts, obtain blocked polyisocyanate composition solution (C-4) 1400 parts.Except the simple and easy grabber of solvent contains 183 parts of isopropanols.The solid component concentration of the blocked polyisocyanate compound solution (C-4) obtained is about 60%.
Additionally, (C-1) and (C-2) be the blocked polyisocyanate compound solution used in embodiment described later, (C-3) and (C-4) is the blocked polyisocyanate compound solution without nonionic hydrophilic group used in comparative example described later.
The manufacture of hydroxy acryl acid resin
Manufacture example 18
The reaction vessel possessing thermometer, thermostat, agitating device, reflux condenser, nitrogen ingress pipe and Dropping feeder adds propylene glycol monopropyl ether 35 parts, after being warming up to 85 DEG C, last 4 hours dropping methyl methacrylates 30 parts, 2-EHA 20 parts, n-butyl acrylate 29 parts, acrylic acid 2-hydroxy methacrylate 15 parts, 6 parts of acrylic acid, propylene glycol monopropyl ether 15 parts and 2,2'-azo double; two (2,4-methyl pentane nitrile) mixture of 2.3 parts, completion of dropwise addition post curing 1 hour.Then last 1 hour dropping propylene glycol monopropyl ether 10 parts and 2, the mixture of 2 '-azo pair (2,4-methyl pentane nitrile) 1 part, completion of dropwise addition post curing 1 hour then,.Add diethanolamine 7.4 parts, obtain the hydroxy acryl acid resin solution (E-1) of solid constituent 55%.The acid number of the hydroxy acryl acid resin obtained is 47mgKOH/g, hydroxyl value is 72mgKOH/g.
The manufacture of hydroxyl group containing polyester resin
Manufacture example 19
The reaction vessel possessing thermometer, thermostat, agitating device, reflux condenser and water separator adds adipic acid 192 parts, hexahydrophthalic anhydride 307 parts, 2-butyl-2-ethyl-1, ammediol 439 parts, 1,6-hexanediol 88.7 parts and trimethylolpropane 36.0 parts, after lasting 3 hours and being warming up to 230 DEG C from 160 DEG C, while utilizing water separator that condensation water is distilled off, while being maintained at 230 DEG C so that it is reaction is until becoming desired acid number.This reaction product adds trimellitic anhydride 20.2 parts, after carrying out additive reaction in 30 minutes at 170 DEG C, it is cooled to less than 50 DEG C, it is neutralized with 2-(dimethylamino) ethanol, it is slowly added deionized water, thus obtains the hydroxyl group containing polyester resin aqueous dispersions (F-1) of solid component concentration 45%.The acid number of the hydroxyl group containing polyester resin obtained is 20mgKOH/g, hydroxyl value be 60mgKOH/g, number-average molecular weight is 1,700.
The making of the 1st pigmented finiss (X)
Manufacture example 20
nullChlorine-free vistanex dispersion liquid (A-1) 35 parts (solid constituent) is coordinated according to conventional method、Waterborne polyurethane resin dispersion liquid (B-1) 20 parts (solid constituent)、There is the blocked polyisocyanate compound solution (C-1) 20 parts (solid constituent) of nonionic hydrophilic group、Hydroxy acryl acid resin solution (E-1) 10 parts (solid constituent)、Hydroxyl group containing polyester resin (F-1) 15 parts (solid constituent)、Conductive pigment (D-1) (" Ketjen black EC600J "，Lyons AudioCodes is helped Co., Ltd. and is manufactured，Trade name，Conductive carbon black pigment) 5 parts、" JR-806 " (Tayca company manufactures，Trade name，Titanium white) 100 parts and mix dispersion，Dilute so that solid constituent is 20% with deionized water，Obtain aqueous the 1st pigmented finiss (X-1).
Manufacture example 21～42
In manufacturing example 20, cooperation composition is set to as shown in table 2, in addition, by operating in the same manner as manufacturing example 20, obtains each aqueous the 1st pigmented finiss (X-2)～(X-23).
Representing it addition, the cooperation of table 2 is solid constituent, (note 2) in table 2 is as shown in following.
(note 2) watersoluble chlorinated polyolefin (A-3) (be 35mgKOH/g by the maleic acid modified acid number obtained and chlorine containing ratio be 22% the aqueous dispersion of maleic acid modified chlorinated polypropylene)
[table 2]
Table 2
Table 2 (Continued)
The manufacture of clear dope (Z)
The manufacture of hydroxy acryl acid resin (K)
Manufacture example 43～50
The four-hole boiling flask possessing agitating device, thermometer, condensing tube, nitrogen inlet adds ethoxyethyl propionate 31 parts, is warming up to 155 DEG C when nitrogen is ventilated.After reaching 155 DEG C, stop nitrogen ventilation, last 4 hours dropping from the monomer shown in Table 3 below and polymerization initiator constitute form with monomer mixture.Then, after passing into nitrogen ripening on one side at 155 DEG C 2 hours, it is cooled to 100 DEG C, is diluted with butyl acetate 32.5 parts, thus obtain hydroxy acryl acid resin (K-1)～(K-8) of solid constituent 60%.The special numerical value of the quality solid constituent concentration (%) of the hydroxy acryl acid resin obtained and resin is shown in Table 3 below.
[table 3]
Table 3
The manufacture of hydroxyl polycarbonate polyester resin (L3)
Manufacture example 51
The reaction unit possessing thermometer, thermostat, blender and heater adds UM-90 (trade name, Yu Buxingchan company manufactures, Merlon ester) 270 parts, 6-caprolactone 136.8 parts, the Dibutyltin oxide appropriate amount of about 1700 (number-average molecular weight of the hydroxyl polycarbonate polyester resin obtained be), stir and be warming up to 170 DEG C.At 170 DEG C, continue reaction, confirm that heating remains in more than 98.5%, carry out cooling down, discharging, obtain hydroxyl polycarbonate polyester resin (L3-1) solution.The number-average molecular weight of hydroxyl polycarbonate polyester resin (L3-1) obtained is 1650.
Manufacture example 52
The reaction unit possessing thermometer, thermostat, blender and heater adds UM-90 (trade name, Yu Buxingchan company manufactures, Merlon ester) 270 parts, 6-caprolactone 136.8 parts, the Dibutyltin oxide appropriate amount of about 2200 (number-average molecular weight of the hydroxyl polycarbonate polyester resin obtained be), stir and be warming up to 170 DEG C.At 170 DEG C, continue reaction, confirm that heating remains in more than 98.5%, carry out cooling down, discharging, obtain hydroxyl polycarbonate polyester resin (L3-2) solution.The number-average molecular weight of hydroxyl polycarbonate polyester resin (L3-2) obtained is 2200.
Manufacture example 53
The reaction unit possessing thermometer, thermostat, blender and heater adds UM-90 (trade name, Yu Buxingchan company manufactures, Merlon ester) 270 parts, 6-caprolactone 136.8 parts, the Dibutyltin oxide appropriate amount of about 3000 (number-average molecular weight of the hydroxyl polycarbonate polyester resin obtained be), stir and be warming up to 170 DEG C.At 170 DEG C, continue reaction, confirm that heating remains in more than 98.5%, carry out cooling down, discharging, obtain hydroxyl polycarbonate polyester resin (L3-3) solution.The number-average molecular weight of hydroxyl polycarbonate polyester resin (L3-3) obtained is 2900.
The making of clear dope (Z)
Manufacture example 54～79
Use the raw material recorded in table 5, with being stirred with the use of vane-type stirring machine and mix shown in aftermentioned table 5.Then, add butyl acetate in the mixture, use Ford cup #No.4 to be adjusted at 20 DEG C the viscosity of 25 seconds, obtain each clear dope (Z-1)～(Z-14).It addition, the cooperation of the clear dope (Z) shown in table 5 is the solid constituent mass ratio of each composition.
Hydroxyl group containing polyester resin (L1-1) and hydroxyl polycarbonate resin (L2-1) in table 5 have following implication.
Hydroxyl group containing polyester resin (L1-1): " Placcel305 " trade name, Diacel chemical industrial company manufactures.Number mean molecule quantity 550.
Hydroxyl polycarbonate resin (L2-1): " UM-90 " trade name, Yu Buxingchan company manufactures, and diol component is 1,4-cyclohexanedimethanol and 1,6-hexanediol, 1, quality/1 of 4-cyclohexanedimethanol, the PCDL of quality=1/1 of 6-hexanediol.Number mean molecule quantity 900.
Described in organo-metallic catalyst (M) table that Details as Follows states 4 in table 5.
[table 4]
Table 4
* chemistry industry companies of 1NikkaOcthixZinc Japan manufactures, Zn content 8%
* 2 zinc naphthenate Tokyo chemical conversion industrial groups manufacture, Zn content 10.1%
* 3 zinc acetylacetonate Showa chemical companies manufacture, Zn content 25%
* 4 dibenzoic acid zinc and Guang Chun medicine industrial group manufacture, Zn content 21.3%
* 5 Dodecanoic acid, zinc salts and Guang Chun medicine industrial group manufacture, Zn content 14.1%
* chemistry industry companies of 6NikkaOcthixTin Japan manufactures, Theil indices 28%
* 7K-KAT348KingIndustries company manufactures, bi content 25%
* 8DBU diazabicyclo endecatylene
Polyisocyanate compounds (PI) in table 5 has following implication.
Polyisocyanate compounds (PI): " SumiduleN3300 " trade name, Zhu Hua BayerUrethane company manufactures, the isocyanuric acid ester body of hexamethylene diisocyanate, solid constituent 100%, NCO containing ratio 21.8%
[table 5]
Table 5
Table 5 (Continued)
I-1. the making of coated plate is tested
As metal parts, in cold-rolled steel sheet (450mm × 300mm × 0.8mm) the substrates application heat-curable epoxy resin cationoid electrodeposition coating composition (trade name " ELECRONGT-10 " that zinc phosphate processed, Northwest paint company manufactures) to make thickness be 20 μm, at 170 DEG C, heating makes it solidify in 30 minutes.
As plastic components, prepare " TSOP-1 (TC-6) " (trade name, Polygem company of Japan manufactures, 350mm × 10mm × 2mm).
Then, ungrease treatment is carried out with the surface of the gauze wiping metal parts containing petroleum benzin and plastic components.By adjacent to the steel plate as above obtained and polypropylene board configuration, as bread board.
In above-mentioned bread board, the 1st pigmented finiss (X-1)～(X-23) of the above-mentioned making of spray-coating makes dry film thickness be 10 μm, after at room temperature standing 6 minutes, electrostatic spraying is as " WBC-713T#1F7 " (trade name of painted base coating, Northwest paint company manufactures, acrylic melamine resinae aqueous overcoating base coating coating, silver color is tinted, and is designated as " (Y-1) " in table 6,7) to make dry film thickness be 15 μm.Then, clear dope (Z-1)～(Z-26) of the above-mentioned making of electrostatic spraying makes dry film thickness be 30 μm, after at room temperature placing 5 minutes, heats 30 minutes, obtain being formed with the test coated plate of multilayer film in the baking oven of 95 DEG C.This multilayer film is utilized to carry out various film performances test (table 6,7) of the following stated.
I-2. film performance test
Retouching property: retouching property is evaluated by following flatness and distinctiveness.
Flatness: use the W1 value recorded by " WaveScanDOI " (trade name, BYKGardner company manufactures) to be evaluated.The flatness in the more little expression painting face of W1 value is more high.
S:W1 value is less than the value of 10.0
A:W1 value is the value of 10.0～20.0
C:W1 value is above the value of 20.0.
Distinctiveness: use the W4 value recorded by " WaveScanDOI " (trade name, BYKGardner company manufactures) to be evaluated.The distinctiveness in the more little expression painting face of W4 value is more high.
S:W4 value is less than the value of 10.0
A:W4 value is the value of 10.0～20.0
C:W4 value is above the value of 20.0.
Chipping resistance: (at slungshot testing machine in the test piece holding station of trade name " Q-G-R gravel meter " (manufacture of QPanel company), test coated plate is set, makes with the angle of 90 degree the granite stones of granularity 6 test coated plate collision with 100g by the compression air of 480kPa～520kPa from the place of distance test (DT) coated plate 30cm at-20 DEG C.Then, by the test coated plate washing obtained, dry, be coated with face adhesive fabric adhesive tape (manufacture of Nichiban Co., Ltd.).Then, peel off above-mentioned adhesive tape, be evaluated based on the area (referred to as peeling off area) that the parts in electro-deposition face and substrate expose.
S: relative to test coated plate area peel off area ratio lower than 5%
A: be more than 5% and lower than 10% relative to the ratio peeling off area of test coated plate area
C: relative to test coated plate area peel off area ratio more than 10%.
Water-fast tack: impregnated 240 hours in the warm water of 40 DEG C by test coated plate, pull out, at 20 DEG C after dry 12 hours, cuts into clathrate with cutter in the way of arriving bottom by the multilayer film of test coated plate, makes the gridiron pattern 100 of size 2mm × 2mm.Then, the adhesive tape of laminating bonding in its surface, at 20 DEG C, quickly peel off the Restzustand of adhesive tape " Invest, Then Investigate " gridiron pattern film, according to following benchmark evaluation resistance to water.
S: gridiron pattern film remains 100, the edge in cutter cutting does not produce the less crimping of film
A: gridiron pattern film remains 100, the edge in cutter cutting produces the less crimping of film
B: gridiron pattern film remains 90～99
C: the residual number of gridiron pattern film is below 89.
Ethanol petrol resistant: illustrate according to parts.
The situation of plastic components: impregnated at 20 DEG C in the experimental liquid of gasoline/methanol=90/10 weight ratio by each test coated plate, observes the painting surface state of the expansion through 30 minutes time, peeling, evaluates under following benchmark.
S: entirely without abnormal,
A: lower than the expansion of 3mm, peeling,
The expansion of B:3mm～below 5mm, peeling,
C: more than the expansion of 5mm, peeling.
The situation of metal parts: impregnated at 40 DEG C in the experimental liquid of gasoline/methanol=90/10 weight ratio by each test coated plate, is observed the painting surface state of the expansion through 60 minutes time, peeling, is evaluated by the benchmark same with the situation of plastics.
Weatherability: use " super xenon test apparatus " (Xu He testing machine company manufactures, weathering tester) in the moistening circulation of test film according to JISK5600-7-7: 18 minutes/2 hours, black panel temperature: carry out promoting atmospheric exposure test to each test coated plate being coated on metal parts when 61 DEG C～65 DEG C.Then, the irradiation time at lamp reaches moment of 1,000 hour, 2,000 hours and 3,000 hours, with cutter, the multilayer film of bread board is cut in the way of arriving bottom clathrate, makes the gridiron pattern 100 of size 2mm × 2mm.Then, the adhesive tape of laminating bonding in its surface, at 20 DEG C, quickly peel off the Restzustand of this adhesive tape " Invest, Then Investigate " gridiron pattern film.
S: gridiron pattern film remains 100, the edge in cutter cutting does not produce the less crimping of film
A: gridiron pattern film remains 100, the edge in cutter cutting produces the less crimping of film
C: the residual number of gridiron pattern film is less than 99.
Pot life (storage period): use the viscosity at 20 DEG C behind 6 hours of the Ford cup #No.4 each clear dope of measurement.Pot life after making coating composition by following reference measurement is also evaluated.
Below the S:35 second
A:36 second～40 seconds
C: gelation
-: unmeasured
[table 6]
Table 6
Table 6 (Continued)
Table 6 (Continued)
[table 7]
Table 7
II-1. the making of coated plate is tested
As metal parts, in cold-rolled steel sheet (450mm × 300mm × 0.8mm) the substrates application heat-curable epoxy resin cationoid electrodeposition coating composition (trade name " ELECRONGT-10 " that zinc phosphate processed, Northwest paint company manufactures) to make thickness be 20 μm, at 170 DEG C, heating makes it solidify in 30 minutes.
As plastic components, prepare " TSOP-1 (TC-6) " (trade name, Polygem company of Japan manufactures, 350mm × 10mm × 2mm).
Then, ungrease treatment is carried out with the surface of the gauze wiping metal parts containing petroleum benzin and plastic components.By adjacent to the steel plate as above obtained and polypropylene board configuration, as bread board.
In above-mentioned bread board, the 1st pigmented finiss (X-1) of the above-mentioned making of spray-coating makes dry film thickness be 10 μm, after at room temperature sizing 6 minutes, electrostatic spraying makes dry film thickness be 15 μm as the 2nd pigmented finiss (Y-1) of painted base coating.Then, the clear dope (Z-15), (Z-17), (Z-19), (Z-24), (Z-25) or (Z-26) of the above-mentioned making of electrostatic spraying makes dry film thickness be 30 μm, after at room temperature placing 5 minutes, the baking oven of 75 DEG C heats 30 minutes, obtains being formed with the test coated plate of multilayer film.This multilayer film is utilized to carry out various film performances test (table 8) of the following stated.
II-2. film performance test
Carry out recording same operation, same evaluation with the project of above-mentioned " test of I-2. film performance ".
[table 8]
Table 8

Claims (8)

1. a method of forming layered coating film, described method is to be sequentially carried out the method for forming layered coating film of following operation:
(1) on the coated article containing metal material and plastic material application aqueous the 1st pigmented finiss (X) and form the operation of the 1st uncured painted film；
(2) on the 1st uncured painted film obtained by operation (1) application aqueous the 2nd pigmented finiss (Y) and form the operation of the 2nd uncured painted film；
(3) on the 2nd uncured painted film obtained by operation (2) transparent paint coating (Z) and form the operation of uncured transparent coating；And
(4) by the 1st uncured painted film formed in operation (1)～(3), the 2nd uncured painted film and uncured transparent coating be heated so that the operation that solidifies of this 3 films simultaneously, it is characterized in that
The described aqueous the 1st pigmented finiss (X) polyolefin-based resins (A) containing chlorine-free, acid number be 1mgKOH/g～30mgKOH/g and at the temperature of 20 DEG C the waterborne polyurethane resin (B) that time is 5 minutes～20 minutes till film forming, the blocked polyisocyanate compound (C) with nonionic hydrophilic group and conductive pigment (D)
Aqueous the 1st pigmented finiss (X) described in application the thickness making it solidify and obtaining are that the cured coating film of the 5 μm average transmittance at wavelength 360nm～420nm place is lower than 1%.
2. method of forming layered coating film according to claim 1, wherein, described clear dope (Z) contains
Hydroxyl value is 140mgKOH/g～210mgKOH/g, weight average molecular weight be 5000～18000 and glass transition temperature be the acrylic resin (K) of hydroxyl of-25 DEG C～20 DEG C.
3. method of forming layered coating film according to claim 2, wherein, described clear dope (Z) contains
To be the polyester resin (L1) of the hydroxyl of 500～2500, number-average molecular weight selected from number-average molecular weight be 500～2500 the polycarbonate resin (L2) of hydroxyl and number-average molecular weight be 500～2500 hydroxyl polycarbonate polyester resin (L3) at least one resin.
4. method of forming layered coating film according to claim 1, wherein, described clear dope (Z)
With the resin solid content quality total amount of clear dope for benchmark, the acrylic resin (K) of the hydroxyl containing 30 mass %～70 mass %；
Relative to the solid constituent total amount of the acrylic resin (K) of hydroxyl, containing at least one resin in the polyester resin (L1) of hydroxyl, the polycarbonate resin (L2) of hydroxyl and the polycarbonate polyester resin (L3) of hydroxyl of below 100 mass %；And
Relative to the solid constituent total amount of the acrylic resin (K) of hydroxyl, the polyisocyanate compounds (PI) containing below 200 mass %.
5. the method for forming layered coating film according to any one of Claims 1 to 4, wherein, the described blocked polyisocyanate compound (C) with nonionic hydrophilic group is the blocked polyisocyanate compound with at least one blocked isocyanate base in the blocked isocyanate base shown in the blocked isocyanate base shown in following formula (I), following formula (II) and the blocked isocyanate base shown in following formula (III)
[chemical formula 1]
In formula (I), R1、R2、R4And R5Represent the alkyl of carbon number 1～12, R independently3Represent the straight-chain of carbon number 1～12 or the alkylidene of branched,
[chemical formula 2]
In formula (II), R2、R3、R4And R5With above-mentioned R2、R3、R4And R5It is identical,
[chemical formula 3]
In formula (III), R2, R3, R4 and R5 are identical with above-mentioned R2, R3, R4 and R5, and R6 represents the alkyl of carbon number 1～12.
6. method of forming layered coating film according to claim 3, it is characterised in that above-mentioned clear dope (Z) possibly together with
The organo-metallic catalyst (M) that is made up of zinc compound and amidine compound and
Selected from beta-diketon class, beta-keto acid esters, malonic acid esters, β position, there is the ketone of hydroxyl, β position has the aldehydes of hydroxyl and β position has in the esters of hydroxyl at least one end-capping reagent (N),
The amount of described organo-metallic catalyst (M) is 0.05 mass %～5 mass % relative to the total amount of (K) composition, at least one being selected from (L1) composition, (L2) composition and (L3) composition and (PI) composition.
7. method of forming layered coating film according to claim 6, it is characterized in that, the amount of described end-capping reagent (N) is 0.7 mass %～25 mass % relative to the solid constituent total amount of (K) composition, at least one being selected from (L1) composition, (L2) composition and (L3) composition and (PI) composition.
8. the method for forming layered coating film according to any one of claim 1～7, wherein, the described coated article containing metal material and plastic material is the coated article assembling metal material and plastic material.
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