WO2009001182A1 - Primer composition - Google Patents

Primer composition Download PDF

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Publication number
WO2009001182A1
WO2009001182A1 PCT/IB2008/001492 IB2008001492W WO2009001182A1 WO 2009001182 A1 WO2009001182 A1 WO 2009001182A1 IB 2008001492 W IB2008001492 W IB 2008001492W WO 2009001182 A1 WO2009001182 A1 WO 2009001182A1
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WO
WIPO (PCT)
Prior art keywords
resin
component
mass
primer
coating
Prior art date
Application number
PCT/IB2008/001492
Other languages
French (fr)
Inventor
Toshiya Kitamura
Hayato Ishibashi
Original Assignee
Basf Coatings Japan Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Coatings Japan Ltd. filed Critical Basf Coatings Japan Ltd.
Publication of WO2009001182A1 publication Critical patent/WO2009001182A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • a primer composition with which primer coatings can be formed which have excellent adhesion to metals such as iron or copper, or steel sheet plated with these, in particular zinc-plated steel sheet, and excellent adhesion to the top coat when polyamide (nylon) resins are used as the top coat, and excellent solvent resistance to gasoline and the like.
  • Metal pipe surface treatment methods wherein there are formed a zinc or zinc and nickel plating layer formed on the outer surface of the metal pipe, a conversion treated layer having a trivalent chromium compound and a phosphate compound as the main components formed on said plating layer, an epoxy resin intermediate layer made up of an epoxy resin paint with an added antirust pigment having a condensed phosphate salt and a magnesium silicate compound as the main components formed on said conversion treated layer, and a resin layer (a layer made up of polyvinyl fluoride resin, poly-vinylidene fluoride resin or polyamide resin) formed on the aforesaid epoxy resin intermediate layer (see for example Patent Reference 2).
  • metal object coating methods which are characterized in that a primer composition made by compounding an inorganic antirust agent into at least one type of binder component selected from the group made up of a binder component (A) containing an epoxy resin and an amino resin and/or phenolic resin; a binder component (B) containing a polyester resin, an epoxy resin and a phenolic resin and a binder (C) containing an ⁇ -olefin/ ⁇ , ⁇ -ethylenically unsaturated carboxylic acid copolymer is coated onto the metal object surface to be coated, and a thermoplastic resin film is formed by coating a thermoplastic resin paint (any of vinyl fluoride resin paint, vinylidene fluoride paint or polyamide resin paint) via the primer coating layer obtained (see for example Patent Reference 5) .
  • a thermoplastic resin paint any of vinyl fluoride resin paint, vinylidene fluoride paint or polyamide resin paint
  • Patent Reference 4 Japanese unexamined patent application JP 9-302226A
  • Patent Reference 5 Republished WO 2003-033173
  • the purpose of the present invention is to provide a primer composition with which primer coatings can be formed which have excellent adhesion to metals such as iron or copper, or steel sheet plated with these, in particular zinc-plated steel sheet, and excellent adhesion to the top coat when polyamide (nylon) resins are used as the top coat, and in particular excellent gasohol resistance.
  • the present invention provides a primer composition, characterized in that it contains (A) a polyamide imide resin, (B) nylon resin beads, (C) an epoxy resin, (D) a polyol resin and (E) a curing agent, and the percentage content of component (A) is 10 to 30 mass %, the percentage content of component (B) is 64 to 19 mass %, the percentage content of component
  • component (C) is 10 to 30 mass %
  • the percentage content of component (D) is 15 to 1 mass %
  • the percentage content of component (E) is 1 to 20 mass %, relative to the total resin solids content of component (A) , component (B) , component (C) , component (D) and component (E) .
  • the present invention provides the primer composition as claimed in claim 1, characterized in that in the aforesaid primer composition the component
  • (D) is an acrylic resin polyol resin and/or a polyester resin polyol resin.
  • the present invention provides a primer composition, characterized in that in the aforesaid primer composition the component (E) is a phenolic resin and/or an amino resin.
  • the present invention provides a primer composition, characterized in that in the aforesaid primer composition is a primer composition used as an undercoat paint for polyamide resin coatings.
  • the primer composition of the present invention is able to form primer coatings which have excellent adhesion to metals such as iron or copper, or steel sheet plated with these, in particular zinc-plated steel sheet, and excellent adhesion to the top coat when polyamide
  • the present invention is a primer composition containing a polyamide imide resin, nylon resin beads, an epoxy resin, a polyol resin and a curing agent.
  • the resin acid value of the polyamide imide resin component (A) used in the present invention is preferably 30 mg KOH/g or less, more preferably 10 mg KOH/g or less. If the acid value exceeds 30 mg KOH/g, the storage stability at 50°C may decrease, which is undesirable .
  • the number average molecular weight of the polyamide imide resin component (A) is preferably 9 000 to 28 000, more preferably 12 000 to 25 000. With a number average molecular weight less than 9 000, the gasohol resistance may decrease, and if it exceeds 28 000, the ease of application may decrease, which is undesirable. Further, the polyamide imide resin component (A) is preferably soluble in solvents .
  • the proportion of component (A) in the present invention is such that it suppresses swelling of the coating when immersed in gasohol and ensures the adhesion of the primer coating after immersion in gasohol .
  • the polyamide imide resin is produced by known production methods, and specifically it is obtained by reacting an at least tribasic polycarboxylic acid (a) having an acid anhydride group, a dibasic dicarboxylic acid (b) , an aromatic isocyanate or aromatic diamine (c) and a lactam (d) in a polar organic solvent.
  • the proportions of (a) to (d) for example the compounding proportion of (a) and (b) , (a)/(b) is preferably the equivalent ratio 4/6 to 9/1, the proportion of (c) is preferably 8 to 16 relative to the total number of carboxyl groups and amino groups of (a) and (b) , and the proportion of (d) is preferably 0.1 to 20 mass % relative to the total weight of (a), (b) and (c) .
  • the reaction is performed by thermal condensation in the temperature range 80 to 150°C in the presence of a polar organic solvent, while removing the carbon dioxide liberated from the reaction system if aromatic isocyanate is used.
  • the reaction time is selected as appropriate depending on the batch scale and the reaction conditions adopted.
  • the polar organic solvent for example N-methyl-2- pyrrolidone, N,N-dimethylformamide, N,N-dimethylacet- amide, dimethyl sulfoxide, ⁇ -butyrolactone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and the like can be used singly or as combinations of two or more, and the quantity thereof used is preferably 1.0 to 5.0 times the polyamide imide resin produced (mass). After completion of the polyamide imide resin synthesis, if aromatic isocyanate was used, isocyanate groups at the resin termini can then be blocked with blocking agents such as alcohols, lactams, oximes and the like. [0015]
  • polyamide imide resins include Vylomax HRlINN, Vylomax 13NX, Vylomax 14ET (all Toyobo Co.), HI-405-30, HPC-5000, HPC-5010S, HPC-5020, HPC-5030, HPC-6000, HPC-6100, HPC-7200 and HPC-9000 (all Hitachi Kasei Co.), and the like.
  • a single type of polyamide imide resin component (A) can be used, or two or more types can be used together.
  • nylon resin beads component (B) used in the present invention is preferably at least 150°C, more preferably at least 170°C. With a melting point less than 150°C, the thermal stability of the resin during high temperature stoving tends to decrease, which is undesirable.
  • the nylon resin beads component (B) are preferably nylon resin beads insoluble in solvents such as alcohols, esters and ketones.
  • the mean particle size of the nylon resin beads component (B) is preferably 5 to 100 ⁇ m, more preferably 10 to 50 ⁇ m. With a particle size less than 5 ⁇ m, the paint viscosity tends to become high, which is undesirable, and if it exceeds 100 ⁇ m, the storage stability tends to decline, which is undesirable.
  • the proportion of the nylon resin beads component (B) in the present invention is such as to ensure adhesion of the primer coating and the polyamide resin coating which is the top coat.
  • nylon resin beads polyamide 6 from ring-opening polymerization of ⁇ -caprolactam, polyamide 66 from condensation polymerization of hexamethylene diamine and adipic acid, polyamide 610 from condensation polymerization of hexamethylene diamine and sebacic acid, polyamide 11 from condensation polymerization of 11-aminoundecanoic acid, polyamide 12 from ring-opening polymerization of ⁇ -laurolactam or from condensation polymerization of 12-aminododecanoic acid and the like are mentioned.
  • nylon resin beads Rilsan Fine Powder D30 NATURELL, Rilsan Fine Powder D40 NATURELL, Rilsan Fine Powder D50 NATURELL, Orgasol 1002DNATl, Orgasol 1002ES4NAT1, Orgasol 2002ES4NAT3, Orgasol 2002ES3NAT3, Orgasol 3501 EDXNADl and 3502DNAD1 (all Arkema Co.), SNP Powder-13, SNP Powder-19 (both Metal Color Co.), A1020LP (Unitika Co.) and the like are mentioned.
  • a single type of nylon resin beads component (B) can be used, or two or more types can be used together.
  • the epoxy value of the epoxy resin component (C) used in the present invention is preferably 30 to 250 mg KOH/g, more preferably 50 to 130 mg KOH/g. If the epoxy value exceeds 250 mg KOH/g, the adhesion to the plated steel sheet tends to decrease, and at less than 30 mg KOH/g, the ease of application tends to decrease.
  • the proportion of the epoxy resin component (C) in the present invention is such as to ensure the adhesion of the primer coating and the plated steel sheet.
  • epoxy resin used in the present invention those having at least two epoxy groups per molecule are preferable, and those previously known, such as liquid epoxy resins and solid epoxy resins, can be used with no particular restrictions. Further, if solid epoxy resins are used, they are used dissolved or dispersed in an organic solvent capable of dissolving or dispersing said resins.
  • bisphenol/epichlorohydrin epoxy resins such as JERlOOl, JER1002, JER1003, JER1055, JER1004, JER1007 (all Japan Epoxy Resin Co.), epotote YD-134, epotote YD-011, epotote YD-012, epotote YD-013, epotote YD-014, epotote YD-017, epotote YD- 7011R, epotote YD-907 (all Tohto Kasei Co.), D. E. R662E, D. E. R663UE, D. E. R664U and D. E.
  • R667E all Dow Chemical Co.
  • a single type of epoxy resin component (C) can be used, or two or more types can be used together.
  • the polyol resin component (D) used in the present invention various polyol resins are mentioned. A single type of polyol resin can be used, or two or more types can be used in combination.
  • polyol resin component (D) polyol resins having a hydroxyl value of 30 to 120 mg KOH/g, preferably 40 to 70 mg KOH/g, a weight average molecular weight of 5 000 to 50 000, preferably 7 000 to 30 000 and an acid value of 0 to 25 mg KOH/g, preferably 0 to 15 mg KOH/g, are preferable.
  • the hydroxyl value of said polyol resin is less than 30 mg KOH/g, the adhesion after immersion in gasohol decreases because of insufficient crosslinking density of the coating obtained, and if it exceeds 120 mg KOH/g, the storage stability of the paint at 4O 0 C decreases, which is undesirable.
  • the weight average molecular weight is less than 5 000, the adhesion after immersion in gasohol decreases because the crosslinking reactions are insufficient, and if it exceeds 50 000, the storage stability of the paint at 40°C decreases, which is undesirable.
  • acrylic resin polyol resins As polyol resins of the present invention, acrylic resin polyol resins, polyester resin polyol resins and the like are mentioned.
  • the acrylic resin polyol resin and polyester resin polyol resin components (D) used in the present invention can each be used singly, and they can also be used mixed.
  • the component (D) of the present invention is such that a crosslinked coating is obtained through reaction with the curing agent component in the compounded resin.
  • the polyol resin is an acrylic resin polyol resin (also referred to as acrylic polyol resin) , this is obtained by polymerizing or copolymerizing another copolymerizable polymerizable unsaturated monomer and/or acrylate ester, using hydroxyl group-containing polymerizable unsaturated monomer (s) stated below as the base.
  • acrylic resin polyol resin also referred to as acrylic polyol resin
  • hydroxyl group-containing polymerizable unsaturated monomers for example hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, 1, 4-butanediol monomethacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, 1, 4-butanediol monoacrylate and the like are mentioned.
  • the 1-18 carbon alkyl alcohols forming the acrylate esters may be alcohols containing linear, branched or cyclic alkyl groups. These can be used singly or as a combination of two or more. [ 0025 ]
  • copolymerizable polymerizable unsaturated monomers, for example phosmer (trade name, Uni-Chemical Co.), glycidyl methacrylate, glycidyl acrylate, allyl methacrylate, allyl acrylate, 3 , 4-epoxycyclohexylmethyl methacrylate, 3 , 4-epoxycyclo-lO-hexylmethyl methacrylate, phenyl methacrylate, phenyl acrylate, ⁇ -methylstyrene, p-vinyltoluene, methacrylamide, acrylamide, N,N-dimethylmethacrylamide, N,N-dimethyl- acrylamide, 2 , 2 , 6, 6-tetramethyl-4-bipyridyl acrylate, aliphatic vinyl ether compounds such as ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-but
  • copolymerizable acrylate esters for example methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, adamantyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, pentyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-
  • copolymerizable unsaturated monomers and copolymerizable acrylate esters are not essential components, and are appropriately selected and used as necessary in the design of coatings, depending on the substrate and the use purpose.
  • organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyneodecanoate, t-butyl peroxy- pivalate, t-hexyl peroxy-2-ethylhexanoate and methyl ethyl ketone hydroperoxide, or azo type initiators such as 2, 2 ' -azobis (2, 4-dimethylvaleronitrile) , 2,2'-azobis- (2-methylpropionitrile) (AIBN) and 2,2'-azobis- (2-methylbutyronitrile) can be mentioned. Of course, they are not restricted to these.
  • the reaction temperature during the radical polymerization is preferably 60 to 150°C. If this temperature is less than 60°C, the radical polymerization initiator decomposes with difficulty and the reaction proceeds with difficulty, and if it exceeds 150°C, even if radicals are formed by thermal decomposition of the radical polymerization initiator, their lifetime is short, and it is difficult for the propagation reaction to proceed efficiently.
  • the polymerization time is influenced by the polymerization temperature and other conditions, and cannot be defined indiscriminately, but about 2 to 6 hours is generally sufficient.
  • the polyol resin component (D) is a polyester resin polyol resin (also referred to as a polyester polyol resin) , it is made by reacting a polybasic acid and a polyhydric alcohol, and as polybasic acids for example phthalic anhydride, tetrahydrophthalic anhydride, isophthalic acid, maleic anhydride, fumaric acid, trimellitic anhydride, methylenetricyclohexenetricarboxylic anhydride, pyro- mellitic anhydride, itaconic acid, adipic acid, sebacic acid, azelaic acid, hexahydrophthalic anhydride, himic anhydride, succinic anhydride, het anhydride and the like are mentioned, and as polyhydric alcohols for example ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, butylene glycol, hexanedio
  • polyester resins can also be modified with monobasic acids, fatty acids, oil components and the like. Furthermore, the introduction of the hydroxyl groups of said polyester resins can easily be effected for example by means of polyhydric alcohols having at least three hydroxyl groups per molecule.
  • the curing agent component (E) used in the present invention phenolic resins and amino resins are preferable, and these can each be used singly or can be used together. The proportion of the component (E) in the present invention is such that it reacts with the resin component in the compounded resin to give a heat curing coating.
  • the number average molecular weight of the phenolic resin is preferably 300 to 1 500, more preferably 400 to 1 000. With a number average molecular weight less than 300, the flexibility of the cured film tends to decrease, and if it exceeds 1 500, the storage stability of the paint at 50°C tends to decrease, which is undesirable. [0031] Phenolic resins are obtained by reacting phenolic species and formaldehyde species .
  • phenolic species used for obtaining phenolic resins for example phenols having one benzene ring in the molecule such as phenol, methylphenol, p-ethylphenol, p-n-propylphenol , p-iso- propylphenol , p-n-butylphenol , p-tert-butylphenol, p-tert-amylphenol, o-cresol, m-cresol, p-cresol, p-cyclohexylphenol , p-octylphenol, p-nonylphenol , 3,5-xylenol, resorcinol and catechol; phenols having two benzene rings in the molecule such as phenyl o-cresol and p-phenylphenol ; bisphenol A, bisphenol F and the like are mentioned, and these can be used singly or as a mixture of two or more.
  • formaldehyde species formaldehyde species
  • the phenolic species can be a resol type phenolic resin or a novolac type phenolic resin. Among these, resol type phenolic resins are ideal. Further, as necessary, it may be a phenolic resin appropriately modified with natural resins, acrylic resins, polyester resins and the like. The aforesaid phenolic resins can be used singly, or two or more can be selected and used together. [0033]
  • the weight average molecular weight of the amino resin is preferably 600 to 20 000, more preferably 1 000 to 10 000. With a weight average molecular weight of less than 800, the flexibility of the cured coating tends to decrease, and if it exceeds 20 000, the gasohol resistance tend to decrease, which is undesirable.
  • amino resins methylolated amino resins obtained by reaction of an amino component, such as melamine resins, urea resins, benzoguanamine resins, aceto- guanamine resins, steroguanamine resins, spiroguanamine resins and dicyandiamide and an aldehyde are mentioned, and the amino resins may also be modified with epoxy resins, acrylic resins, polyester resins and the like. In terms of bending workability, melamine resins are preferable.
  • the aforesaid amino resins can be used singly, or two or more can be selected and used together.
  • curing agent component (E) can be used singly, or two or more types can be used together.
  • the percentage contents of polyamide imide resin component (A) , nylon resin bead component (B) , epoxy resin component (C) and curing agent (D) in the primer composition are component (A) 10 to 30 mass %, component (B) 64 to 19 mass %, component (C) 10 to 30 mass %, component (D) 15 to 1 mass % and component (E) 1 to 20 mass %, relative to the total resin solids content of component (A) , component (B) , component (C) and component (D) .
  • the total of the percentage contents of component (A) , component (B) , component (C) , component (D) and component (E) is 100 mass %.
  • the resin solids content refers to the residue on heating measured by the method described in JIS K5601-1-2.
  • component (A) is less than 10 mass %, the adhesion of primer coating and top coat after immersion in gasohol (secondary adhesion) decreases, and if it exceeds 30 mass %, the initial adhesion of primer coating and top coat (primary adhesion) decreases, which is undesirable.
  • component (B) is less than 19 mass %, the primary adhesion of primer coating and top coat decreases, and if it exceeds 64 mass %, the secondary adhesion of primer coating and top coat after immersion in gasohol decreases, which is undesirable.
  • component (C) is less than 10 mass %, the adhesion of primer coating and plated steel sheet decreases, and if it exceeds 30 mass %, the bending workability decreases, which is undesirable.
  • component (D) is less than 1 mass %, the primary adhesion of primer coating and top coat decreases, and if it exceeds 15 mass %, the secondary adhesion of primer coating and top coat after immersion in gasohol decreases, which is undesirable.
  • component (E) is less than 1 mass %, the adhesion of primer coating and top coat after immersion in gasohol decreases, and if it exceeds 20 mass %, the bending workability decreases, which is undesirable.
  • antirust pigments can be incorporated into the primer compositions of the present invention.
  • the antirust pigments the antirust pigments normally used in undercoat paints can be used.
  • antirust pigments for example chromium pigments such as zinc chromate and strontium chromate, and non-chromium-containing, non-polluting antirust pigments can all be used, but in terms of environmental preservation, the use of non-polluting antirust pigments is preferable.
  • non-polluting antirust pigments for example condensed phosphate salt antirust pigments such as zinc phosphate antirust pigments, magnesium phosphate antirust pigments, aluminum phosphate antirust pigments, calcium phosphate antirust pigments, zinc phosphite antirust pigments, magnesium phosphite antirust pigments, calcium phosphite antirust pigments and aluminum phosphite antirust pigments; pigments made by treating the surface of condensed phosphate salts with metal compounds; zinc antirust pigments such as zinc molybdate antirust pigments, zinc cyanamide antirust pigments and zinc calcium cyanamide antirust pigments; silica and the like are mentioned. These can be used singly or as mixtures of two or more. [0038]
  • Pigments previously used for paints can be added as necessary to the primer composition of the present invention.
  • organic pigments for example azo lake pigments, phthalocyanine pigments, indigo pigments, perylene pigments, quinophthalone pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, metal complex pigments and the like are mentioned.
  • inorganic pigments for example yellow iron oxide, red iron oxide, titanium dioxide, carbon black and the like are mentioned.
  • flake pigments such as aluminum pigments or pearl pigments can also be incorporated. There is no particular restriction as to these pigments, and they can be used singly or as mixtures of two or more .
  • each of components (A) , (C) , (D) and (E) are preferably used dissolved or dispersed in an organic solvent.
  • organic solvent hexane, heptane, isooctane, unsaturated aliphatic hydrocarbons, benzene, toluene, xylene, (o-, m- and p-) cyclohexanone, dioxane, tetra- hydrofuran, cellosolve, methyl cellosolve, butyl cellosolve, methylcarbitol, 2-methoxyethanol 2-butoxy- ethanol diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, triethylene glycol monomethyl ether, l-methoxy-2-propanol, l-ethoxy-2- propanol, dipropylene glycol mono
  • metal sheet such as iron or copper, or plated steel sheet plated with these are preferably used, and zinc plated steel sheet is particularly preferable.
  • a coating pretreatment is preferably performed on the surface of the material, this coating pretreatment can be any conversion treatment used as a pretreatment for precoating metals, and for example chromate conversion treatment, phosphate salt conversion treatment, multiple oxide film treatment and the like are mentioned. [ 0041 ]
  • this can be effected by various coating methods, and for example coating methods using roller coaters, flow coaters, dipping, sprays or the like can be used. Among these, coating with a roller coater is preferable in terms of obtaining film thickness control and uniformity.
  • the coatings obtained by applying the primer compositions can usually be stoved under the curing conditions
  • curing can usually be effected under the curing conditions: material maximum attained temperature 120 to 260°C, for 15 to 120 sees.
  • the dry coating thickness of the primer coating obtained by applying the primer composition of the present invention is preferably usually in the range 1 to 10 ⁇ m, more preferably 3 to 7 ⁇ m.
  • a polyamide (nylon) resin coating is preferable in terms of adhesion.
  • polyamide (nylon) resin polyamide 6 from ring-opening polymerization of ⁇ -caprolactam, polyamide 66 from condensation polymerization of hexamethylene diamine and adipic acid, polyamide 610 from condensation polymerization of hexamethylene diamine and sebacic acid, polyamide 11 from condensation polymerization of 11-aminoundecanoic acid, polyamide 12 from ring-opening polymerization of ⁇ -laurolactam or from condensation polymerization of 12-aminododecanoic acid and the like of the same compositions as the nylon resin beads used in the primer compositions of the present invention are mentioned.
  • the method for forming the polyamide resin coating for example the method of forming the coating by heating at a temperature above the melting point of the polyamide resin and making the melted material into sheet form is mentioned, but it is not restricted
  • the thickness of the polyamide resin coating is preferably 50 to 200 ⁇ m, more preferably 80 to 150 ⁇ m.
  • the primer composition was diluted to Ford Cup No.4 60 sees (25°C) with dilution solvent (50/50 (mass ratio) N- methylpyrrolidone/isophorone solvent mixture) , and this diluted primer composition was applied onto the surface of zinc electroplated steel sheet (length 100 mm, width 67 mm, thickness 0.3 mm) with a bar coater to give a dry coating thickness of 4 to 6 ⁇ m.
  • the ease of application of the primer composition was then assessed by assessing the texture of the primer coating according to the following standards. ++: no problems.
  • the primer composition was diluted to Ford Cup No.4 60 sees (25°C) with dilution solvent (50/50 (mass ratio) N- methylpyrrolidone/isophorone solvent mixture) , and this diluted primer composition was applied onto the surface of zinc electroplated steel sheet (length 100 mm, width 67 mm, thickness 0.3 mm) with a bar coater to give a dry coating thickness of 4 to 6 ⁇ m, and then immediately stove cured for 40 sees at 260°C. During this, a region about 40 mm in length not coated with the primer composition was created.
  • dilution solvent 50/50 (mass ratio) N- methylpyrrolidone/isophorone solvent mixture
  • nylon pellets brand name: Rilsan B BMF O (Arkema Co.) were fused at 300°C, and applied to 100 to 110 ⁇ m thickness with an applicator. During this, a continuous film was also simultaneously applied to the region not coated with the primer composition, to give the test plates. Longitudinal cuts 10 mm wide were made in the coating on the test plates obtained, the nylon coating was pulled at constant speed from the region not coated with the primer composition, and the peeling status of the region coated with the primer composition was assessed according to the following standards. [0046]
  • the primer composition was diluted to Ford Cup No.4 60 sees (25°C) with dilution solvent (50/50 (mass ratio) N- methylpyrrolidone/isophorone solvent mixture) , and this diluted primer composition was applied onto the surface of zinc electroplated steel sheet (length 100 mm, width 67 mm, thickness 0.3 mm) with a bar coater to give a dry coating thickness of 4 to 6 ⁇ m, and then immediately stove cured for 40 sees at 260°C, to give the flexibility test plates.
  • dilution solvent 50/50 (mass ratio) N- methylpyrrolidone/isophorone solvent mixture
  • the primer composition was diluted to Ford Cup No.4 60 sees (25 0 C) with dilution solvent (50/50 (mass ratio) N- methylpyrrolidone/isophorone solvent mixture) , and this diluted primer composition was applied onto the surface of zinc electroplated steel sheet (length 100 mm, width 67 mm, thickness 0.3 mm) with a bar coater to give a dry coating thickness of 4 to 6 ⁇ m, and then immediately stove cured for 40 sees at 260 0 C. During this, a region about 40 nun in length not coated with the primer composition was created.
  • nylon pellets brand name: Rilsan B BMF 0 (Arkema Co.) were fused at 300°C, and applied to 100 to 110 ⁇ m thickness with an applicator. During this, a continuous film was also simultaneously applied to the region not coated with the primer composition, to give the test plates. After immersion of the test plates obtained in gasohol for 120 hrs at 2O 0 C, longitudinal cuts 10 mm wide were made in the coating, the nylon coating was pulled at constant speed from the region not coated with the primer composition, and the peeling status of the region coated with the primer composition was assessed according to the following standards. ++: nylon coating ruptures in primer coated region. +: nylon coating ruptures after cohesion breakdown or interface peeling in primer coated region. X: peeling at interface or cohesion breakdown in primer coated region, but nylon coating does not rupture . [0051]
  • Resin Production Example 1 (Production of acrylic resin polyol resin solution D-I) 300 parts of xylene are placed in a 2 L glass flask fitted with thermometer, stirrer, reflux condenser and a monomer drip feed device, and gradually heated to reflux.
  • Vylomax HRlINN polyamide imide resin, brand name, Toyobo Co., number average molecular weight 15 000, resin solids content 15%
  • barium sulfate SS-50 substantially pigment, brand name, Sakai Chemical Co.
  • matting agent HK125 antirust pigment, brand name, Degussa Co.
  • 50 parts of N-methylpyrrolidone and 50 parts of isophorone are placed in a disperser, and dispersed until the particle size is 30 ⁇ m or less.
  • Vylomax HR13NX polyamide imide resin, brand name, Toyobo Co., number average molecular weight 10 000, resin solids content 30 mass %)
  • 147.2 parts of Orgasol 2002ES3NAT3 nylon resin beads, Arkema Co., mean particle size 40 ⁇ m
  • jERlOOl epoxy resin, brand name, Japan Epoxy Resin Co., epoxy value 118, resins solids content 100 mass %)
  • 25.6 parts of Yuban 20SB melamine resin, brand name, Mitsui Chemical Co.
  • Vylomax HRlINN polyamide imide resin, brand name
  • Orgasol 2002ES4NAT3 nylon resin beads, brand name
  • Arkema Co. mean particle size 40 ⁇ m.
  • Orgasol 2002ES3NAT3 nylon resin beads, brand name
  • Arkema Co. mean particle size 30 ⁇ m.
  • JER1002 epoxy resin, brand name, Japan Epoxy Resin Co., epoxy value 87, resin solids content 100 mass %.
  • JER834 epoxy resin, brand name, Japan Epoxy Resin
  • Shonol CRG-951 phenolic resin, Showa Kobunshi Co., number average molecular weight 750, resin solids content 100 mass %.
  • Yuban 80S melamine resin, brand name, Mitsui
  • Yuban 20SB melamine resin, brand name, Mitsui Chemical Co., weight average molecular weight 5 780, resin solids content 50 mass %.
  • Yuban 122 melamine resin, brand name, Mitsui Chemical Co., weight average molecular weight 1 560, resin solids content 60 mass %.
  • Matting agent HK-125 antirust pigment, brand name, Degussa Co.
  • Ti-Pure R-706 titanium oxide, brand name, Dupont Co.
  • Carbon black FW200 carbon black, brand name
  • JER828 epoxy resin, brand name, Japan Epoxy Resin Co., epoxy value 297, resin solids content 100 mass %.
  • Comparative Examples 1-4 if the percentage content of the polyamide imide resin, nylon resin beads or polyol resin is outside the claimed range, the initial adhesion of the top coat to the primer coating or the adhesion of the top coat to the primer coating after immersion in gasohol becomes poor. Further, as shown in Comparative Examples 5-6, if the percentage content of the epoxy resin is outside the claimed range, the adhesion of the primer coating and the plated steel sheet becomes poor, or the flexibility becomes poor. Furthermore, as shown in Comparative Examples 7-8, if the percentage content of the curing agent is outside the claimed range, the adhesion of the top coat to the primer coating after immersion in gasohol or the flexibility becomes poor. [ 0071 ]
  • primer compositions useful as undercoats for polyamide resin coatings are obtained, which have excellent primer composition ease of application, and with which primer coatings with excellent adhesion of plated steel sheet and primer coating (primary adhesion) , initial adhesion of primer coating and top coat (primary adhesion) , flexibility and adhesion of primer coating and top coat after immersion in gasohol (secondary adhesion) can be formed.

Abstract

To provide a primer composition with which primer coatings can be formed which have excellent adhesion to metals such as iron or copper, or steel sheet plated with these, in particular zinc-plated steel sheet, and excellent adhesion to the top when polyamide (nylon) resins are used as the top coat, and, in particular excellent gasohol resistance. [Means of Solving Problem] A primer composition, characterized in that it contains (A) a polyamide imide resin, (B) nylon resin beads, (C) an epoxy resin, (D) a polyol resin and (E) a curing agent, and the percentage content of component (A) is 10 to 30 mass %, the percentage content of component (B) is 64 to 19 mass %, the percentage content of component (C) is 10 to 30 mass %, the percentage content of component (D) is 15 to 1 mass %, and the percentage content of component (E) is 1 to 20 mass %, relative to the total resin solids content of component (A), component (B), component (C), component (D) and component (E).

Description

Primer composition
[Technological Field] [0001]
It relates to a primer composition with which primer coatings can be formed which have excellent adhesion to metals such as iron or copper, or steel sheet plated with these, in particular zinc-plated steel sheet, and excellent adhesion to the top coat when polyamide (nylon) resins are used as the top coat, and excellent solvent resistance to gasoline and the like. [Background Technology] [0002] As the piping of automobile brake systems, fuel systems or hydraulic systems, piping is known which is characterized in that the external plastic jacket layer is a layer made up of a thermoplastic material, in particular a polyamide resin, extruded on top of a chromate layer on the outer surface of an inner metal pipe (see for example Patent Reference 1) . However, this piping had the disadvantage that the adhesion was unsatisfactory after immersion in gasohol (gasoline mixed with a low concentration of ethanol; a fuel developed and brought into use in the USA and Brazil with the aim of decreasing octane number improvement and nitrogen dioxide emissions) . [0003] Metal pipe surface treatment methods are known wherein there are formed a zinc or zinc and nickel plating layer formed on the outer surface of the metal pipe, a conversion treated layer having a trivalent chromium compound and a phosphate compound as the main components formed on said plating layer, an epoxy resin intermediate layer made up of an epoxy resin paint with an added antirust pigment having a condensed phosphate salt and a magnesium silicate compound as the main components formed on said conversion treated layer, and a resin layer (a layer made up of polyvinyl fluoride resin, poly-vinylidene fluoride resin or polyamide resin) formed on the aforesaid epoxy resin intermediate layer (see for example Patent Reference 2). However, this method had the disadvantage that, although the treatment and coating do not involve hexavalent chromium, they do involve trivalent chromium, and cannot be stated to be completely chromium-free as the market requires, and the disadvantage that adhesion after immersion in gasohol was unsatisfactory. [0004]
Further, with regard to pipes for liquids used in automobiles, in particular for fuel and hydraulic fluid, made up of a metal inner pipe, an aluminum coat formed on the outside of the inner pipe and a polyamide layer coupled to the aluminum coat, methods are known wherein a non-chromium-containing surface-treated layer and/or a primer coat using a commercial polyamide is interposed (see for example Patent Reference 3) . However, there was a disadvantage in that the gasohol resistance (coating adhesion test after immersion in gasohol) was unsatisfactory. [0005] Further, it is known that low temperature curing and high adhesion are obtained by adding epoxy resin to polyamide imide resins (see for example Patent Reference 4) . However, there was a disadvantage in that the coating was brittle and its bending workability was unsatisfactory. [0006]
Further, metal object coating methods are known which are characterized in that a primer composition made by compounding an inorganic antirust agent into at least one type of binder component selected from the group made up of a binder component (A) containing an epoxy resin and an amino resin and/or phenolic resin; a binder component (B) containing a polyester resin, an epoxy resin and a phenolic resin and a binder (C) containing an α-olefin/α, β-ethylenically unsaturated carboxylic acid copolymer is coated onto the metal object surface to be coated, and a thermoplastic resin film is formed by coating a thermoplastic resin paint (any of vinyl fluoride resin paint, vinylidene fluoride paint or polyamide resin paint) via the primer coating layer obtained (see for example Patent Reference 5) .
However, this method has the disadvantage that the gasohol resistance of the multilayer coating coated with polyamide resin paint is unsatisfactory.
[0007]
[Patent Reference 1] Japanese unexamined patent application JP 9-509723
[Patent Reference 2] Japanese unexamined patent application JP 2003-194288A
[Patent Reference 3] Japanese unexamined patent application JP 2003-343767A
[Patent Reference 4] Japanese unexamined patent application JP 9-302226A [Patent Reference 5] Republished WO 2003-033173
[Disclosure of Invention]
[Problem to be Solved by Invention]
[0008]
The purpose of the present invention is to provide a primer composition with which primer coatings can be formed which have excellent adhesion to metals such as iron or copper, or steel sheet plated with these, in particular zinc-plated steel sheet, and excellent adhesion to the top coat when polyamide (nylon) resins are used as the top coat, and in particular excellent gasohol resistance. [Means of Solving Problem] [0009] The present inventors, as a result of repeated and diligent studies, discovered that the aforesaid problem is solved by means of a primer composition containing a polyamide imide resin, nylon resin beads, epoxy resin, polyol resin and curing agent in specific proportions, and thus accomplished the present invention.
In other words, the present invention provides a primer composition, characterized in that it contains (A) a polyamide imide resin, (B) nylon resin beads, (C) an epoxy resin, (D) a polyol resin and (E) a curing agent, and the percentage content of component (A) is 10 to 30 mass %, the percentage content of component (B) is 64 to 19 mass %, the percentage content of component
(C) is 10 to 30 mass %, the percentage content of component (D) is 15 to 1 mass %, and the percentage content of component (E) is 1 to 20 mass %, relative to the total resin solids content of component (A) , component (B) , component (C) , component (D) and component (E) . [0010]
Further, the present invention provides the primer composition as claimed in claim 1, characterized in that in the aforesaid primer composition the component
(D) is an acrylic resin polyol resin and/or a polyester resin polyol resin.
Further, the present invention provides a primer composition, characterized in that in the aforesaid primer composition the component (E) is a phenolic resin and/or an amino resin.
Further, the present invention provides a primer composition, characterized in that in the aforesaid primer composition is a primer composition used as an undercoat paint for polyamide resin coatings. [Effect of Invention] [0011]
The primer composition of the present invention is able to form primer coatings which have excellent adhesion to metals such as iron or copper, or steel sheet plated with these, in particular zinc-plated steel sheet, and excellent adhesion to the top coat when polyamide
(nylon) resins are used as the top coat, and in particular excellent gasohol resistance. [Optimal Means of Implementing Invention] [0012]
The present invention is a primer composition containing a polyamide imide resin, nylon resin beads, an epoxy resin, a polyol resin and a curing agent.
The resin acid value of the polyamide imide resin component (A) used in the present invention is preferably 30 mg KOH/g or less, more preferably 10 mg KOH/g or less. If the acid value exceeds 30 mg KOH/g, the storage stability at 50°C may decrease, which is undesirable .
Further, the number average molecular weight of the polyamide imide resin component (A) is preferably 9 000 to 28 000, more preferably 12 000 to 25 000. With a number average molecular weight less than 9 000, the gasohol resistance may decrease, and if it exceeds 28 000, the ease of application may decrease, which is undesirable. Further, the polyamide imide resin component (A) is preferably soluble in solvents .
The proportion of component (A) in the present invention is such that it suppresses swelling of the coating when immersed in gasohol and ensures the adhesion of the primer coating after immersion in gasohol . [0013] There is no particular restriction as to the method for production of the polyamide imide resin, and various methods are mentioned. The polyamide imide resin is produced by known production methods, and specifically it is obtained by reacting an at least tribasic polycarboxylic acid (a) having an acid anhydride group, a dibasic dicarboxylic acid (b) , an aromatic isocyanate or aromatic diamine (c) and a lactam (d) in a polar organic solvent. As the proportions of (a) to (d) , for example the compounding proportion of (a) and (b) , (a)/(b) is preferably the equivalent ratio 4/6 to 9/1, the proportion of (c) is preferably 8 to 16 relative to the total number of carboxyl groups and amino groups of (a) and (b) , and the proportion of (d) is preferably 0.1 to 20 mass % relative to the total weight of (a), (b) and (c) . The reaction is performed by thermal condensation in the temperature range 80 to 150°C in the presence of a polar organic solvent, while removing the carbon dioxide liberated from the reaction system if aromatic isocyanate is used. The reaction time is selected as appropriate depending on the batch scale and the reaction conditions adopted. [0014] As the polar organic solvent, for example N-methyl-2- pyrrolidone, N,N-dimethylformamide, N,N-dimethylacet- amide, dimethyl sulfoxide, γ-butyrolactone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and the like can be used singly or as combinations of two or more, and the quantity thereof used is preferably 1.0 to 5.0 times the polyamide imide resin produced (mass). After completion of the polyamide imide resin synthesis, if aromatic isocyanate was used, isocyanate groups at the resin termini can then be blocked with blocking agents such as alcohols, lactams, oximes and the like. [0015]
Commercial polyamide imide resins include Vylomax HRlINN, Vylomax 13NX, Vylomax 14ET (all Toyobo Co.), HI-405-30, HPC-5000, HPC-5010S, HPC-5020, HPC-5030, HPC-6000, HPC-6100, HPC-7200 and HPC-9000 (all Hitachi Kasei Co.), and the like.
A single type of polyamide imide resin component (A) can be used, or two or more types can be used together.
[0016]
The melting point of the nylon resin beads component
(B) used in the present invention is preferably at least 150°C, more preferably at least 170°C. With a melting point less than 150°C, the thermal stability of the resin during high temperature stoving tends to decrease, which is undesirable. Further, the nylon resin beads component (B) are preferably nylon resin beads insoluble in solvents such as alcohols, esters and ketones.
Further, the mean particle size of the nylon resin beads component (B) is preferably 5 to 100 μm, more preferably 10 to 50 μm. With a particle size less than 5 μm, the paint viscosity tends to become high, which is undesirable, and if it exceeds 100 μm, the storage stability tends to decline, which is undesirable.
The proportion of the nylon resin beads component (B) in the present invention is such as to ensure adhesion of the primer coating and the polyamide resin coating which is the top coat. [0017]
As the nylon resin beads, polyamide 6 from ring-opening polymerization of ε-caprolactam, polyamide 66 from condensation polymerization of hexamethylene diamine and adipic acid, polyamide 610 from condensation polymerization of hexamethylene diamine and sebacic acid, polyamide 11 from condensation polymerization of 11-aminoundecanoic acid, polyamide 12 from ring-opening polymerization of ω-laurolactam or from condensation polymerization of 12-aminododecanoic acid and the like are mentioned. [0018] As commercial nylon resin beads, Rilsan Fine Powder D30 NATURELL, Rilsan Fine Powder D40 NATURELL, Rilsan Fine Powder D50 NATURELL, Orgasol 1002DNATl, Orgasol 1002ES4NAT1, Orgasol 2002ES4NAT3, Orgasol 2002ES3NAT3, Orgasol 3501 EDXNADl and 3502DNAD1 (all Arkema Co.), SNP Powder-13, SNP Powder-19 (both Metal Color Co.), A1020LP (Unitika Co.) and the like are mentioned. A single type of nylon resin beads component (B) can be used, or two or more types can be used together. [0019]
The epoxy value of the epoxy resin component (C) used in the present invention is preferably 30 to 250 mg KOH/g, more preferably 50 to 130 mg KOH/g. If the epoxy value exceeds 250 mg KOH/g, the adhesion to the plated steel sheet tends to decrease, and at less than 30 mg KOH/g, the ease of application tends to decrease.
The proportion of the epoxy resin component (C) in the present invention is such as to ensure the adhesion of the primer coating and the plated steel sheet. [0020]
As the epoxy resin used in the present invention, those having at least two epoxy groups per molecule are preferable, and those previously known, such as liquid epoxy resins and solid epoxy resins, can be used with no particular restrictions. Further, if solid epoxy resins are used, they are used dissolved or dispersed in an organic solvent capable of dissolving or dispersing said resins. [0021]
As commercial epoxy resins, bisphenol/epichlorohydrin epoxy resins such as JERlOOl, JER1002, JER1003, JER1055, JER1004, JER1007 (all Japan Epoxy Resin Co.), epotote YD-134, epotote YD-011, epotote YD-012, epotote YD-013, epotote YD-014, epotote YD-017, epotote YD- 7011R, epotote YD-907 (all Tohto Kasei Co.), D. E. R662E, D. E. R663UE, D. E. R664U and D. E. R667E (all Dow Chemical Co.) and the like are mentioned. A single type of epoxy resin component (C) can be used, or two or more types can be used together. [0022] As the polyol resin component (D) used in the present invention, various polyol resins are mentioned. A single type of polyol resin can be used, or two or more types can be used in combination.
As the polyol resin component (D) , polyol resins having a hydroxyl value of 30 to 120 mg KOH/g, preferably 40 to 70 mg KOH/g, a weight average molecular weight of 5 000 to 50 000, preferably 7 000 to 30 000 and an acid value of 0 to 25 mg KOH/g, preferably 0 to 15 mg KOH/g, are preferable.
If the hydroxyl value of said polyol resin is less than 30 mg KOH/g, the adhesion after immersion in gasohol decreases because of insufficient crosslinking density of the coating obtained, and if it exceeds 120 mg KOH/g, the storage stability of the paint at 4O0C decreases, which is undesirable.
If the weight average molecular weight is less than 5 000, the adhesion after immersion in gasohol decreases because the crosslinking reactions are insufficient, and if it exceeds 50 000, the storage stability of the paint at 40°C decreases, which is undesirable.
If the acid value exceeds 25 mg KOH/g, the storage stability of the paint at 400C decreases, which is undesirable . [ 0023 ]
As polyol resins of the present invention, acrylic resin polyol resins, polyester resin polyol resins and the like are mentioned.
The acrylic resin polyol resin and polyester resin polyol resin components (D) used in the present invention can each be used singly, and they can also be used mixed.
The component (D) of the present invention is such that a crosslinked coating is obtained through reaction with the curing agent component in the compounded resin. [0024]
If the polyol resin is an acrylic resin polyol resin (also referred to as acrylic polyol resin) , this is obtained by polymerizing or copolymerizing another copolymerizable polymerizable unsaturated monomer and/or acrylate ester, using hydroxyl group-containing polymerizable unsaturated monomer (s) stated below as the base.
As hydroxyl group-containing polymerizable unsaturated monomers, for example hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, 1, 4-butanediol monomethacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, 1, 4-butanediol monoacrylate and the like are mentioned. Further, the 1-18 carbon alkyl alcohols forming the acrylate esters may be alcohols containing linear, branched or cyclic alkyl groups. These can be used singly or as a combination of two or more. [ 0025 ]
As the other copolymerizable polymerizable unsaturated, monomers, for example phosmer (trade name, Uni-Chemical Co.), glycidyl methacrylate, glycidyl acrylate, allyl methacrylate, allyl acrylate, 3 , 4-epoxycyclohexylmethyl methacrylate, 3 , 4-epoxycyclo-lO-hexylmethyl methacrylate, phenyl methacrylate, phenyl acrylate, α-methylstyrene, p-vinyltoluene, methacrylamide, acrylamide, N,N-dimethylmethacrylamide, N,N-dimethyl- acrylamide, 2 , 2 , 6, 6-tetramethyl-4-bipyridyl acrylate, aliphatic vinyl ether compounds such as ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether and cyclohexyl vinyl ether, and also 2, 3-dihydrofuran, 3 , 4-dihydro-2H-pyran, trimethoxy- silylpropyl methacrylate, maleic anhydride, itaconic anhydride, maleate esters, fumarate esters, styrene, acrylonitrile, methacrylonitrile, 2-hydroxyethyl crotonate, 2-hydroxypropyl crotonate, 3-hydroxypropyl crotonate, 3-hydroxybutyl crotonate, 4-hydroxybutyl crotonate, 5-hydroxypentyl crotonate and 6-hydroxyhexyl crotonate, allyl group-containing compounds such as allyl alcohol and allyl glycidyl ether, alkyl esters of crotonic acid such as methyl crotonate, ethyl crotonate and propyl crotonate, vinyl esters of aliphatic carboxylic acids such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl hexanoate, vinyl octanoate, vinyl decanoate, vinyl laurate and vinyl stearate, vinyl esters of alicyclic carboxylic acids such as vinyl cyclohexanecarboxylate, vinyl esters of aromatic carboxylic acids such as vinyl benzoate, vinyl cinnamate and vinyl p-t-butylbenzoate and the like are mentioned. These can be used singly or as a combination of two or more. [0026]
As examples of copolymerizable acrylate esters, for example methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, adamantyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, pentyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-ethyl- hexyl acrylate, adamantyl acrylate, dodecyl acrylate, isobornyl acrylate, methacrylic acid, acrylic acid, itaconic acid, mesaconic acid, maleic acid, fumaric acid, ω-carboxy-polycaprolactone (n=2) monoacrylate (for example Aronix M-5300 (brand name, Toa Gosei Co.)), monohydroxyethyl acrylate phthalate (for example Aronix M-5400 (brand name, Toa Gosei Co.)), acrylic acid dimer (for example Aronix M-5600 (brand name, Toa Gosei Co.)) and the like are mentioned. These can be used singly or as a combination of two or more. [0027]
The other copolymerizable unsaturated monomers and copolymerizable acrylate esters are not essential components, and are appropriately selected and used as necessary in the design of coatings, depending on the substrate and the use purpose.
There is no particular restriction as to the method for polymerizing or copolymerizing the hydroxyl group- containing polymerisable unsaturated monomers and the like, and known methods, for example solution polymerization in a suitable solvent, suspension polymerization, emulsion polymerization, bulk polymer- ization, precipitation polymerization and the like can be used. Further, there is no particular restriction as to the polymerization system, and for example any of radical polymerization, cationic polymerization and anionic polymerization can be used, however, from the industrial viewpoint, among these, radical polymerization is ideal. As polymerization initiators used in the radical polymerization, for example organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyneodecanoate, t-butyl peroxy- pivalate, t-hexyl peroxy-2-ethylhexanoate and methyl ethyl ketone hydroperoxide, or azo type initiators such as 2, 2 ' -azobis (2, 4-dimethylvaleronitrile) , 2,2'-azobis- (2-methylpropionitrile) (AIBN) and 2,2'-azobis- (2-methylbutyronitrile) can be mentioned. Of course, they are not restricted to these. These radical polymerization initiators can be used singly or as a combination of two or more. [0028] In general, the reaction temperature during the radical polymerization is preferably 60 to 150°C. If this temperature is less than 60°C, the radical polymerization initiator decomposes with difficulty and the reaction proceeds with difficulty, and if it exceeds 150°C, even if radicals are formed by thermal decomposition of the radical polymerization initiator, their lifetime is short, and it is difficult for the propagation reaction to proceed efficiently. The polymerization time is influenced by the polymerization temperature and other conditions, and cannot be defined indiscriminately, but about 2 to 6 hours is generally sufficient. [0029]
Further, if the polyol resin component (D) is a polyester resin polyol resin (also referred to as a polyester polyol resin) , it is made by reacting a polybasic acid and a polyhydric alcohol, and as polybasic acids for example phthalic anhydride, tetrahydrophthalic anhydride, isophthalic acid, maleic anhydride, fumaric acid, trimellitic anhydride, methylenetricyclohexenetricarboxylic anhydride, pyro- mellitic anhydride, itaconic acid, adipic acid, sebacic acid, azelaic acid, hexahydrophthalic anhydride, himic anhydride, succinic anhydride, het anhydride and the like are mentioned, and as polyhydric alcohols for example ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, butylene glycol, hexanediol, trimethylolethane, trimethylol- propane, pentaerythritol, dipentaerythritol , sorbitol and the like are mentioned. Furthermore, said polyester resins can also be modified with monobasic acids, fatty acids, oil components and the like. Furthermore, the introduction of the hydroxyl groups of said polyester resins can easily be effected for example by means of polyhydric alcohols having at least three hydroxyl groups per molecule. [0030] As the curing agent component (E) used in the present invention, phenolic resins and amino resins are preferable, and these can each be used singly or can be used together. The proportion of the component (E) in the present invention is such that it reacts with the resin component in the compounded resin to give a heat curing coating.
The number average molecular weight of the phenolic resin is preferably 300 to 1 500, more preferably 400 to 1 000. With a number average molecular weight less than 300, the flexibility of the cured film tends to decrease, and if it exceeds 1 500, the storage stability of the paint at 50°C tends to decrease, which is undesirable. [0031] Phenolic resins are obtained by reacting phenolic species and formaldehyde species . As phenolic species used for obtaining phenolic resins, for example phenols having one benzene ring in the molecule such as phenol, methylphenol, p-ethylphenol, p-n-propylphenol , p-iso- propylphenol , p-n-butylphenol , p-tert-butylphenol, p-tert-amylphenol, o-cresol, m-cresol, p-cresol, p-cyclohexylphenol , p-octylphenol, p-nonylphenol , 3,5-xylenol, resorcinol and catechol; phenols having two benzene rings in the molecule such as phenyl o-cresol and p-phenylphenol ; bisphenol A, bisphenol F and the like are mentioned, and these can be used singly or as a mixture of two or more. Further, as formaldehyde species, formaldehyde, paraformaldehyde, trioxane and the like are mentioned. [0032]
In the reaction of the aforesaid phenolic species and formaldehyde species, inorganic acids, organic acids, organic acid metal salts and the like can be used as catalysts . The phenolic species can be a resol type phenolic resin or a novolac type phenolic resin. Among these, resol type phenolic resins are ideal. Further, as necessary, it may be a phenolic resin appropriately modified with natural resins, acrylic resins, polyester resins and the like. The aforesaid phenolic resins can be used singly, or two or more can be selected and used together. [0033]
Further, the weight average molecular weight of the amino resin is preferably 600 to 20 000, more preferably 1 000 to 10 000. With a weight average molecular weight of less than 800, the flexibility of the cured coating tends to decrease, and if it exceeds 20 000, the gasohol resistance tend to decrease, which is undesirable.
As amino resins, methylolated amino resins obtained by reaction of an amino component, such as melamine resins, urea resins, benzoguanamine resins, aceto- guanamine resins, steroguanamine resins, spiroguanamine resins and dicyandiamide and an aldehyde are mentioned, and the amino resins may also be modified with epoxy resins, acrylic resins, polyester resins and the like. In terms of bending workability, melamine resins are preferable. The aforesaid amino resins can be used singly, or two or more can be selected and used together.
One type of curing agent component (E) can be used singly, or two or more types can be used together.
[0034]
The percentage contents of polyamide imide resin component (A) , nylon resin bead component (B) , epoxy resin component (C) and curing agent (D) in the primer composition, are component (A) 10 to 30 mass %, component (B) 64 to 19 mass %, component (C) 10 to 30 mass %, component (D) 15 to 1 mass % and component (E) 1 to 20 mass %, relative to the total resin solids content of component (A) , component (B) , component (C) and component (D) .
More preferably, they are component (A) 15-22 mass %, component (B) 57-25 mass %, component (C) 15-25 mass %, component (D) 12-2 mass % and component (E) 3-13 mass %.
The total of the percentage contents of component (A) , component (B) , component (C) , component (D) and component (E) is 100 mass %. Also, the resin solids content refers to the residue on heating measured by the method described in JIS K5601-1-2. [0035]
If the component (A) is less than 10 mass %, the adhesion of primer coating and top coat after immersion in gasohol (secondary adhesion) decreases, and if it exceeds 30 mass %, the initial adhesion of primer coating and top coat (primary adhesion) decreases, which is undesirable.
If the component (B) is less than 19 mass %, the primary adhesion of primer coating and top coat decreases, and if it exceeds 64 mass %, the secondary adhesion of primer coating and top coat after immersion in gasohol decreases, which is undesirable. If the component (C) is less than 10 mass %, the adhesion of primer coating and plated steel sheet decreases, and if it exceeds 30 mass %, the bending workability decreases, which is undesirable.
If the component (D) is less than 1 mass %, the primary adhesion of primer coating and top coat decreases, and if it exceeds 15 mass %, the secondary adhesion of primer coating and top coat after immersion in gasohol decreases, which is undesirable.
If the component (E) is less than 1 mass %, the adhesion of primer coating and top coat after immersion in gasohol decreases, and if it exceeds 20 mass %, the bending workability decreases, which is undesirable.
[0036]
In order to increase corrosion resistance, antirust pigments can be incorporated into the primer compositions of the present invention. As the antirust pigments, the antirust pigments normally used in undercoat paints can be used.
As specific antirust pigments, for example chromium pigments such as zinc chromate and strontium chromate, and non-chromium-containing, non-polluting antirust pigments can all be used, but in terms of environmental preservation, the use of non-polluting antirust pigments is preferable. [0037]
As non-polluting antirust pigments, for example condensed phosphate salt antirust pigments such as zinc phosphate antirust pigments, magnesium phosphate antirust pigments, aluminum phosphate antirust pigments, calcium phosphate antirust pigments, zinc phosphite antirust pigments, magnesium phosphite antirust pigments, calcium phosphite antirust pigments and aluminum phosphite antirust pigments; pigments made by treating the surface of condensed phosphate salts with metal compounds; zinc antirust pigments such as zinc molybdate antirust pigments, zinc cyanamide antirust pigments and zinc calcium cyanamide antirust pigments; silica and the like are mentioned. These can be used singly or as mixtures of two or more. [0038]
Pigments previously used for paints, such as inorganic pigments other than antirust pigments, organic pigments, treated pigments and the like, can be added as necessary to the primer composition of the present invention. As organic pigments, for example azo lake pigments, phthalocyanine pigments, indigo pigments, perylene pigments, quinophthalone pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, metal complex pigments and the like are mentioned. Further, as inorganic pigments, for example yellow iron oxide, red iron oxide, titanium dioxide, carbon black and the like are mentioned.
Further, if necessary, flake pigments such as aluminum pigments or pearl pigments can also be incorporated. There is no particular restriction as to these pigments, and they can be used singly or as mixtures of two or more . [0039]
In the primer compositions of the present invention, each of components (A) , (C) , (D) and (E) are preferably used dissolved or dispersed in an organic solvent. As said organic solvent, hexane, heptane, isooctane, unsaturated aliphatic hydrocarbons, benzene, toluene, xylene, (o-, m- and p-) cyclohexanone, dioxane, tetra- hydrofuran, cellosolve, methyl cellosolve, butyl cellosolve, methylcarbitol, 2-methoxyethanol 2-butoxy- ethanol diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, triethylene glycol monomethyl ether, l-methoxy-2-propanol, l-ethoxy-2- propanol, dipropylene glycol monomethyl ether, acetone methyl ethyl ketone, isophorone, cyclohexanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, 3-methoxybutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclo- hexyl acetate, ethylene glycol monoacetate, cellosolve acetate, carbitol acetate, ethyl acetoacetate, pyridine, N-methyl-2-pyrrolidone, formamide, N, N- dimethylformamide, acetamide and the like are mentioned. [0040]
As materials onto which the primer compositions of the present invention are applied, metal sheet such as iron or copper, or plated steel sheet plated with these are preferably used, and zinc plated steel sheet is particularly preferable. When the primer compositions of the present invention are applied, a coating pretreatment is preferably performed on the surface of the material, this coating pretreatment can be any conversion treatment used as a pretreatment for precoating metals, and for example chromate conversion treatment, phosphate salt conversion treatment, multiple oxide film treatment and the like are mentioned. [ 0041 ]
As regards methods for applying the primer composition of the present invention, this can be effected by various coating methods, and for example coating methods using roller coaters, flow coaters, dipping, sprays or the like can be used. Among these, coating with a roller coater is preferable in terms of obtaining film thickness control and uniformity. The coatings obtained by applying the primer compositions can usually be stoved under the curing conditions
100 to 300°C for 5 sees to 5 mins , and for example in the field of precoating paints applied with a roller coater, curing can usually be effected under the curing conditions: material maximum attained temperature 120 to 260°C, for 15 to 120 sees.
The dry coating thickness of the primer coating obtained by applying the primer composition of the present invention is preferably usually in the range 1 to 10 μm, more preferably 3 to 7 μm. [0042]
As the coating which is applied on top of the primer paint coating of the present invention, a polyamide (nylon) resin coating is preferable in terms of adhesion. As the polyamide (nylon) resin, polyamide 6 from ring-opening polymerization of ε-caprolactam, polyamide 66 from condensation polymerization of hexamethylene diamine and adipic acid, polyamide 610 from condensation polymerization of hexamethylene diamine and sebacic acid, polyamide 11 from condensation polymerization of 11-aminoundecanoic acid, polyamide 12 from ring-opening polymerization of ω-laurolactam or from condensation polymerization of 12-aminododecanoic acid and the like of the same compositions as the nylon resin beads used in the primer compositions of the present invention are mentioned. As the method for forming the polyamide resin coating, for example the method of forming the coating by heating at a temperature above the melting point of the polyamide resin and making the melted material into sheet form is mentioned, but it is not restricted to this, and various methods may be mentioned.
The thickness of the polyamide resin coating is preferably 50 to 200 μm, more preferably 80 to 150 μm.
[Practical Examples]
[0043]
Below, the present invention is more specifically explained by means of production examples, practical examples and comparative examples. It should be noted that the present invention is not restricted to these practical examples. Below, unless especially stated, "parts" and "%" respectively mean "mass parts" and "mass %" . Further, in Tables 1 to 3 , the units of the numerical values showing the quantities of each component incorporated are mass parts .
Also, in the practical examples and comparative examples, the assessment of the various headings was performed by the following methods. [ 0044 ]
Method for Assessing the Ease of Application and the Coating Ease of Application of Primer Composition
The primer composition was diluted to Ford Cup No.4 60 sees (25°C) with dilution solvent (50/50 (mass ratio) N- methylpyrrolidone/isophorone solvent mixture) , and this diluted primer composition was applied onto the surface of zinc electroplated steel sheet (length 100 mm, width 67 mm, thickness 0.3 mm) with a bar coater to give a dry coating thickness of 4 to 6 μm. The ease of application of the primer composition was then assessed by assessing the texture of the primer coating according to the following standards. ++: no problems.
+: no problems in practical use.
X: uneven texture formed, problems in practical use. [0045]
Primary Adhesive Performance
The primer composition was diluted to Ford Cup No.4 60 sees (25°C) with dilution solvent (50/50 (mass ratio) N- methylpyrrolidone/isophorone solvent mixture) , and this diluted primer composition was applied onto the surface of zinc electroplated steel sheet (length 100 mm, width 67 mm, thickness 0.3 mm) with a bar coater to give a dry coating thickness of 4 to 6 μm, and then immediately stove cured for 40 sees at 260°C. During this, a region about 40 mm in length not coated with the primer composition was created.
Next, nylon pellets (brand name: Rilsan B BMF O (Arkema Co.) were fused at 300°C, and applied to 100 to 110 μm thickness with an applicator. During this, a continuous film was also simultaneously applied to the region not coated with the primer composition, to give the test plates. Longitudinal cuts 10 mm wide were made in the coating on the test plates obtained, the nylon coating was pulled at constant speed from the region not coated with the primer composition, and the peeling status of the region coated with the primer composition was assessed according to the following standards. [0046]
(i) Adhesion of primer coating to plated steel sheet ++: nylon coating ruptures in primer coated region. +: nylon coating ruptures after cohesion breakdown or interface peeling in primer coated region. X: peeling at interface of plated steel sheet and primer coating, but nylon coating does not rupture. [0047] (ii) Initial adhesion of top coat to primer coating Test plates were made in the same manner as for the adhesion of the primer coating to the plated steel sheet (primary adhesion) , and the initial adhesion of the top coat to the primer coating (primary adhesion) was assessed according to the following standards ++: nylon coating ruptures in primer coated region. +: nylon coating ruptures after cohesion breakdown or interface peeling in primer coated region. X: peeling at interface of primer coating and nylon coating, but nylon coating does not rupture. [0048]
Flexibility
The primer composition was diluted to Ford Cup No.4 60 sees (25°C) with dilution solvent (50/50 (mass ratio) N- methylpyrrolidone/isophorone solvent mixture) , and this diluted primer composition was applied onto the surface of zinc electroplated steel sheet (length 100 mm, width 67 mm, thickness 0.3 mm) with a bar coater to give a dry coating thickness of 4 to 6 μm, and then immediately stove cured for 40 sees at 260°C, to give the flexibility test plates.
For the flexibility testing, at room temperature 20°C, with test pieces cut to 5 cm width, 180° bending was effected with no sandwiching in OT, sandwiching on the inside with 1 coated plate identical to the test piece in IT, and 2 coated plates identical to the test piece in 2T, with the coating on the outside, and 180° bending was effected with sandwiching on the inside with 4 identical plates in 4T, with the coating on the outside. These flexibility test results were assessed on the basis of the following standards. ++: no crack formation at 4T. +: slight cracking on 4T bending, but no problems in practical use.
X: cracks form, problems in practical use. [0049] Adhesion of top coat to primer coat after immersion in gasohol (secondary adhesion)
The primer composition was diluted to Ford Cup No.4 60 sees (250C) with dilution solvent (50/50 (mass ratio) N- methylpyrrolidone/isophorone solvent mixture) , and this diluted primer composition was applied onto the surface of zinc electroplated steel sheet (length 100 mm, width 67 mm, thickness 0.3 mm) with a bar coater to give a dry coating thickness of 4 to 6 μm, and then immediately stove cured for 40 sees at 2600C. During this, a region about 40 nun in length not coated with the primer composition was created. [0050] Next, nylon pellets (brand name: Rilsan B BMF 0 (Arkema Co.) were fused at 300°C, and applied to 100 to 110 μm thickness with an applicator. During this, a continuous film was also simultaneously applied to the region not coated with the primer composition, to give the test plates. After immersion of the test plates obtained in gasohol for 120 hrs at 2O0C, longitudinal cuts 10 mm wide were made in the coating, the nylon coating was pulled at constant speed from the region not coated with the primer composition, and the peeling status of the region coated with the primer composition was assessed according to the following standards. ++: nylon coating ruptures in primer coated region. +: nylon coating ruptures after cohesion breakdown or interface peeling in primer coated region. X: peeling at interface or cohesion breakdown in primer coated region, but nylon coating does not rupture . [0051]
Resin Production Example 1 (Production of acrylic resin polyol resin solution D-I) 300 parts of xylene are placed in a 2 L glass flask fitted with thermometer, stirrer, reflux condenser and a monomer drip feed device, and gradually heated to reflux. While maintaining refluxing, a mixed solution of 60 parts of styrene, 90 parts of butyl acrylate, 120 parts of methyl methacrylate, 204 parts of butyl methacrylate, 120 parts of hydroxyethyl methacrylate, 6 parts of acrylic acid and 11 parts of polymerization initiator Perbutyl Z (brand name, Nippon Oils and Fats Co.; t-butyl peroxybenzoate) was added dropwise from the drip feed device, which required 3 hrs . Next, after completion of the dropwise addition, 1 part of Perbutyl Z and 10 parts of xylene were mixed, and added dropwise from the drip feed device over the course of 3 hours . The reaction was continued for a further 2 hrs while maintaining reflux temperature, and on addition of 78 parts of xylene and cooling to room temperature, acrylic resin polyol resin solution D-I with a resins solids content of 61 mass % was obtained. The raw material weights incorporated and the properties of the acrylic resin polyol resin obtained are shown in Table 1.
[0052]
Resin Production Example 2 (Production of acrylic resin polyol resin solution D-2)
The acrylic resin polyol resin solution D-2 shown in Table 1 was obtained in the same manner as in resin Production Example 1. The raw material weights incorporated and the properties of the acrylic resin polyol resin obtained are shown in Table 1. [0053] Resin Production Example 3 (Production of polyester resin polyol resin solution D-3)
187.3 parts of butyl ethyl propanediol, 18.8 parts of trimethylolpropane, 94 parts of 1, 6-hexanediol, 31.3 parts of phthalic anhydride, and 295.2 parts of adipic acid were placed in a 2 L glass flask fitted with a thermometer and stirrer, and gradually heated to
140°C, then heated to 190°C over 3 hrs. After promoting the esterification reaction by maintaining at 1900C for 2 hrs, the mixture was heated to 210°C over 2 hrs, and the esterification reaction carried out until the resin acid value was 10 or below. The resin obtained was cooled, and on addition of 373.4 parts of xylene, polyester resin polyol resin solution D-3 with a solids content of 60 mass % was obtained. The raw material weights incorporated and the properties of the polyester resin polyol resin obtained are shown in Table 2. [0054]
Primer Composition Production Example P-I 381.8 parts of Vylomax HRlINN (polyamide imide resin, brand name, Toyobo Co., number average molecular weight 15 000, resin solids content 15%), 9.5 parts of barium sulfate SS-50 (substantive pigment, brand name, Sakai Chemical Co.), 22.3 parts of matting agent HK125 (antirust pigment, brand name, Degussa Co.), 50 parts of N-methylpyrrolidone and 50 parts of isophorone are placed in a disperser, and dispersed until the particle size is 30 μm or less. When the desired particle size is reached, the dispersion is stopped, and 165.5 parts of Rilsan Fine Powder D30 NATURELL (nylon resin beads, brand name, Arkema Co., mean particle size 25 μm) , a solvent made by mixing 50 parts of N-methylpyrrolidone and 50 parts of isophorone and a solution made by dissolving 57.3 parts of JERlOOl (epoxy resin, brand name, Japan Epoxy Resin Co., epoxy value 118, resins solids content 100 mass %) , and 20.9 parts of acrylic resin polyol resin D-I, 21.6 parts of Shonol CKS-704
(phenolic resin, Showa Kobunshi Co., number average molecular weight 430, resin solids content 59 mass %) , 25.5 parts of Yuban 80S (melamine resin, brand name, Mitsui Chemical Co., weight average molecular weight 3 700, resin solids content 50 mass %) , 47.8 parts of N-methylpyrrolidone and 47.8 parts of isophorone were added, and on stirring thoroughly, primer composition production example P-I, shown in Table 3, was obtained. It should be noted that the numerical values for residue on heating stated in the properties column for the primer compositions shown in Tables 3-5 show the percentage content of residue on heating (mass %) relative to the total mass of the primer compositions, the residue on heating is made up of resin and pigment, and if the numerical values of the percentage content of resin and pigment (mass %) are added, this gives the percentage content (mass %) of the residue on heating. [0055]
Primer Composition Production Examples P-2 to P-3 and P-5 to P-22 P-2 to P-3, and P-5 to P-22, shown in Tables 3 to 5, were obtained in the same manner as primer composition production example P-I. [0056]
Primer Composition Production Example P-4 224 parts of Vylomax HR13NX (polyamide imide resin, brand name, Toyobo Co., number average molecular weight 10 000, resin solids content 30 mass %) , 147.2 parts of Orgasol 2002ES3NAT3 (nylon resin beads, Arkema Co., mean particle size 40 μm) , a solvent made by mixing 50 parts of N-methylpyrrolidone and 50 parts of isophorone, a solution made by dissolving 64 parts of jERlOOl (epoxy resin, brand name, Japan Epoxy Resin Co., epoxy value 118, resins solids content 100 mass %) , and 26.2 parts of acrylic resin polyol resin D-2, 21.7 parts of Shonol CKS-704 (phenolic resin, Showa Kobunshi Co., number average molecular weight 430, resin solids content 59 mass %) , 25.6 parts of Yuban 20SB (melamine resin, brand name, Mitsui Chemical Co., weight average molecular weight 5 780, resin solids content 50 mass %) , 195.7 parts of N-methylpyrrolidone and 195.6 parts of isophorone were placed in a stirred device, and stirred thoroughly to give primer composition production example P-4, shown in Table 3.
[ 0057 ]
Practical Example 1
Using primer composition production example P-I, the ease of application of the primer composition was assessed by the methods stated in "ease of application of primer compositions", and the results are shown in Table 4. Next, the flexibility was assessed by the methods stated in "flexibility", and the results are shown in Table 4. Next, the adhesion was assessed by the methods stated in "adhesion of primer coating to plated steel sheet (primary adhesion) " and "adhesion of top coat to primer coating (primary adhesion)", and the results are shown in Table 4. Further, the adhesion was assessed by the method stated in "adhesion of top coat to primer coating after immersion in gasohol (secondary adhesion)", and the results are shown in Table 6. [0058] Practical Examples 2-14, Comparative Examples 1-8
The different headings were assessed in the same manner as in Practical Example 1, and the results are summarized in Table 6 and Table 7.
[0059] [Table 1]
Figure imgf000034_0001
[0060] [Table 2]
Figure imgf000034_0002
[0061] [Table 3]
Figure imgf000035_0001
[0062] [Table 4]
Figure imgf000036_0001
[ 0063 ] [ Table 5 ]
Figure imgf000037_0001
[0064]
The numerals with appended brackets in the tables have the following meanings:
1) : Vylomax HRlINN: polyamide imide resin, brand name,
Toyobo Co., number average molecular weight 10 000, resin solids content 15 mass %.
2): Vylomax HR13NX: polyamide imide resin, brand name,
Toyobo Co., number average molecular weight 10 000, resin solids content 30 mass %.
3): HI-405-30: polyamide imide resin, brand name,
Hitachi Kasei Co., number average molecular weight
19 000, resin solids content 30 mass %.
4) : Rilsan Fine Powder D30 NATURELL: solvent-insoluble nylon resin beads, brand name, Arkema Co., mean particle size 25 μm.
5): Orgasol 2002ES4NAT3: nylon resin beads, brand name,
Arkema Co., mean particle size 40 μm.
[0065] 6): Orgasol 2002ES3NAT3: nylon resin beads, brand name
Arkema Co., mean particle size 30 μm.
7): jERlOOl: epoxy resin, brand name, Japan Epoxy Resin
Co., epoxy value 118, resin solids content 100 mass %.
8): JER1002: epoxy resin, brand name, Japan Epoxy Resin Co., epoxy value 87, resin solids content 100 mass %.
9): JER834: epoxy resin, brand name, Japan Epoxy Resin
Co., epoxy value 226, resin solids content 100 mass %.
10): YD-907: epoxy resin, brand name, Tohto Kasei Co., epoxy value 38, resin solids content 100 mass%. [0066]
11): Shonol CKS-704: phenolic resin, Showa Kobunshi
Co., number average molecular weight 430, resin solids content 59 mass %.
12): Shonol CRG-951: phenolic resin, Showa Kobunshi Co., number average molecular weight 750, resin solids content 100 mass %.
13): Yuban 80S: melamine resin, brand name, Mitsui
Chemical Co., weight average molecular weight 3 700, resin solids content 50 mass %.
14) : Yuban 20SB: melamine resin, brand name, Mitsui Chemical Co., weight average molecular weight 5 780, resin solids content 50 mass %.
15): Yuban 122: melamine resin, brand name, Mitsui Chemical Co., weight average molecular weight 1 560, resin solids content 60 mass %. [0067] 16): Barium sulfate SS-50: substantive pigment, brand name, Sakai Chemical Co.
17): Matting agent HK-125: antirust pigment, brand name, Degussa Co. 18): Ti-Pure R-706: titanium oxide, brand name, Dupont Co.
19): Carbon black FW200: carbon black, brand name,
Degussa Co.
20): JER828: epoxy resin, brand name, Japan Epoxy Resin Co., epoxy value 297, resin solids content 100 mass %. [0068]
[Table 6]
Figure imgf000039_0001
[0069] [Table 7]
Comparative Example primer composition production example No P-15 P-16 P-17 P-18 P-19 P-20 P-21 P-22 pπmer composition ease of appication © © adhesion of pπmer coating to plated steel sheet (pπmary adhesion) © adhesion of top coat to pπmer coating
X (pπmary adhesion) O © flexibiity O O adhesion of top coat to pπmer coating after immersion in gasohol (secondary adhesion) © O ©
[ 0070 ] As shown in Practical Examples 1-14 in Table 6, with the primer compositions of the present invention, provided that they are within the claimed range of the present invention, performance at at least the level where there are no problems in practical use is obtained in all cases.
However, as shown in Comparative Examples 1-4, if the percentage content of the polyamide imide resin, nylon resin beads or polyol resin is outside the claimed range, the initial adhesion of the top coat to the primer coating or the adhesion of the top coat to the primer coating after immersion in gasohol becomes poor. Further, as shown in Comparative Examples 5-6, if the percentage content of the epoxy resin is outside the claimed range, the adhesion of the primer coating and the plated steel sheet becomes poor, or the flexibility becomes poor. Furthermore, as shown in Comparative Examples 7-8, if the percentage content of the curing agent is outside the claimed range, the adhesion of the top coat to the primer coating after immersion in gasohol or the flexibility becomes poor. [ 0071 ]
As stated above, if each component of the primer composition is within the claimed range, primer compositions useful as undercoats for polyamide resin coatings are obtained, which have excellent primer composition ease of application, and with which primer coatings with excellent adhesion of plated steel sheet and primer coating (primary adhesion) , initial adhesion of primer coating and top coat (primary adhesion) , flexibility and adhesion of primer coating and top coat after immersion in gasohol (secondary adhesion) can be formed.

Claims

Claims
[Claim 1] A primer composition, characterized in that it contains (A) a polyamide imide resin, (B) nylon resin beads, (C) an epoxy resin, (D) a polyol resin and (E) a curing agent, and the percentage content of component (A) is 10 to 30 mass %, the percentage content of component (B) is 64 to 19 mass %, the percentage content of component (C) is 10 to 30 mass %, the percentage content of component (D) is 15 to 1 mass %, and the percentage content of component (E) is 1 to 20 mass %, relative to the total resin solids content of component (A) , component (B) , component (C) , component (D) and component (E) . [Claim 2]
The primer composition as claimed in claim 1, characterized in that the component (D) is an acrylic resin polyol resin and/or a polyester resin polyol resin. [Claim 3]
The primer composition as claimed in claims 1 or 2, characterized in that the component (E) is a phenolic resin and/or an amino resin. [Claim 4]
The primer composition as claimed in any of claims 1 to 3, characterized in that it is a primer composition used as an undercoat paint for polyamide resin coatings.
PCT/IB2008/001492 2007-06-22 2008-06-04 Primer composition WO2009001182A1 (en)

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US9107727B2 (en) 2001-08-27 2015-08-18 Boston Scientific Scimed, Inc. Satiation devices and methods
US9254214B2 (en) 2001-08-27 2016-02-09 Boston Scientific Scimed, Inc. Satiation devices and methods
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CN107073898A (en) * 2014-11-10 2017-08-18 三樱工业株式会社 Vehicle piping clad metallic pipe
US10337660B2 (en) 2014-11-10 2019-07-02 Sanoh Industrial Co., Ltd. Coated metal pipe for vehicle piping
CN106318089A (en) * 2016-08-17 2017-01-11 安徽红桥金属制造有限公司 Quick-dry tight metal paint surface repairing agent

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