CN102791483B - Zinc-plated steel sheet having coating film formed thereon and having excellent white rust resistance - Google Patents

Zinc-plated steel sheet having coating film formed thereon and having excellent white rust resistance Download PDF

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Publication number
CN102791483B
CN102791483B CN201180013465.5A CN201180013465A CN102791483B CN 102791483 B CN102791483 B CN 102791483B CN 201180013465 A CN201180013465 A CN 201180013465A CN 102791483 B CN102791483 B CN 102791483B
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film
coating composition
resin
mass parts
galvanized steel
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CN102791483A (en
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松田英树
林真弘
三好裕也
村田理章
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Kansai Paint Co Ltd
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Kansai Paint Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)
  • Coating With Molten Metal (AREA)

Abstract

Disclosed is a zinc-plated steel sheet having a coating film formed thereon, in which a multi-layered coating film composed of a non-chromium coating composition is formed on both the front surface and the rear surface thereof, and which has excellent corrosion resistance in a flat area and excellent resistance to white rust in a processed part and an edge part (which is highly visible particularly in the initial stage in use). Specifically disclosed is a zinc-plated steel sheet having a coating film formed thereon, in which a multi-layered coating film is formed on the front surface thereof and a one-layered or multi-layered coating film is formed on the rear surface thereof. In the steel sheet, a coating film composed of a coating composition that comprises a hydroxy-group-containing coating-film-forming resin and contains a predetermined amount of an anti-corrosion pigment is formed on the lowermost layer of at least one of the front and rear surfaces thereof, and a coating film composed of a coating composition that contains a predetermined amount of a silicic acid ion of a metal silicate salt and a metal ion exchange silica, a phosphoric acid group and/or a phosphate salt group of a phosphoric-acid-group-containing coating-film-forming resin and/or a phosphate-salt-group-containing coating-film-forming resin, and/or an azole compound is formed on the uppermost layer of at least one of the front and rear surfaces.

Description

Have excellent resistance to white rust its on be formed with the galvanized steel plain sheet of film
Technical field
The present invention relates to the galvanized steel plain sheet being formed with film, wherein all form the multilayer film be made up of non-chromium class coating composition on the front and back, and it has excellent corrosion resistance.More specifically, the present invention be more particularly directed to the galvanized steel plain sheet being formed with film in processing department and end face portion with excellent resistance to white rust.
Background technology
The galvanized steel plain sheet that the pre-coated steel plate etc. such as applied by coil coating etc. is formed with film has been widely used as the article relevant to house, the roof of such as building, wall, the construction material such as shutter and garage, various household electrical appliance, distribution board, refrigerator-freezer, steel furniture and cooking apparatus.
Prepared in the process of these article relevant to house by the galvanized steel plain sheet being formed with film, usually cutting, pressing mold connect the galvanized steel plain sheet that pre-coated steel plate etc. is formed with film.Therefore, these article relevant to house metal exposed portion of being usually produced as cut surface and the crack that causes due to pressure processing.These metal exposed portions and crack are tending towards poorer than other parts in corrosion resistance.Therefore, the conventional method carried out improves corrosion resistance by being joined by chromium rust resisting pigment in the priming coat that formed on the galvanized steel plain sheet being formed with film.Chromium rust resisting pigment comprises or produces the Cr VI with excellent anticorrosive property.But this Cr VI has problems in human health and environmental protection.
Suggested the multiple coating composition of the mixture comprising non-chromium class pigment, and thereon by applying that such coating composition forms film, that there is excellent corrosion resistance various metals material.
Such as, PTL1 discloses and obtains coating composition by adding rust resisting pigment in the film formative resin of hydroxyl, and this rust resisting pigment is the mixture of the specific vfanadium compound of special ratios, special metal silicate and specific phosphoric acid hydrogen slaine.
PTL2 discloses the metal material being formed with film of the anti-rust coating formed on the front and back had at metal material, this film comprises the anticorrosive coating composition obtained by adding rust resisting pigment in the film formative resin of hydroxyl, and this anti-corrosion paint is the mixture of the specific vfanadium compound of special ratios, specific material and the calcium salt based on phosphoric acid.
The metal material with the film be made up of the coating composition described in PTL1 and PTL2 has excellent corrosion resistance usually; But, and have by compared with the metal material of the film using the coating composition of chromium pigment to form, particularly when metal material is galvanized steel plain sheet, exist and especially produce the problem of a large amount of white rust at the use initial stage in end face portion.In addition, the generation of white rust can not be suppressed fully.
Reference listing
Patent document
PTL 1: the 2008-291160 Japanese Unexamined Patent Publication
PTL 2: the 2000-266444 Japanese Unexamined Patent Publication
Summary of the invention
Technical problem
The object of this invention is to provide the galvanized steel plain sheet being formed with film, it has the film be made up of non-chromium coatings composition all formed on the front and back, described plate not only has excellent corrosion resistance in planar portions, and in processing department and end face portion, there is excellent resistance to white rust, this is especially can be observable at the use initial stage.
The scheme of dealing with problems
As for solving the problem and the result of the extensive research carried out, the present inventor finds that this problem can be solved by the galvanized steel plain sheet being formed with film all on the front and back with film, wherein on the bottom of at least one of front and back, form the film be made up of coating composition, this coating composition comprises the film formative resin of hydroxyl and the rust resisting pigment of specified quantitative, and in the superiors of at least one of front and back, form the film be made up of coating composition, this coating composition comprises the film formative resin of hydroxyl and at least one compound being selected from metal silicate and metal ion exchanged silica of specified quantitative, be selected from least one resin and/or the azole compounds of the film formative resin of phosphoric acid group and the film formative resin of phosphate-containing group.Therefore, the present invention completes.
More specifically, the invention provides down and list:
1. galvanized steel plain sheets being formed with film, described in be formed with film galvanized steel plain sheet in its front, there is multilayer film and at its back side, there is one or more layers film; Wherein
The bottom of at least one of described front and back is formed the coating be made up of following coating composition (I), and in the superiors of at least one of described front and back, forms the coating be made up of following coating composition (II):
coating composition (I): be the coating composition comprising the film formative resin (A) of hydroxyl, crosslinking agent (B) and rust resisting pigment (C), wherein, based on the described resin (A) of 100 mass parts and the total solids content of described crosslinking agent (B), the amount of described rust resisting pigment (C) is 10 mass parts to 150 mass parts; And
coating composition (II): be comprise the film formative resin (A) of hydroxyl and the coating composition of crosslinking agent (B); Wherein,
Described coating composition (II) also comprises at least one compound (Da) being selected from metal silicate and metal ion exchanged silica, and based on the described resin (A) of 100 mass parts and the total solids content of described crosslinking agent (B), the amount of described compound (Da) is 3 mass parts to 50 mass parts; Or,
Described coating composition (II) also comprises at least one resin (Db) of the film formative resin of film formative resin and the phosphate-containing group being selected from phosphoric acid group, and based on the described resin (A) of 100 mass parts and the total solids content of described crosslinking agent (B), the amount of described resin (Db) is 5 mass parts to 30 mass parts; Or,
Described coating composition (II) also comprises azole compounds (Dc), and based on the described resin (A) of 100 mass parts and the total solids content of described crosslinking agent (B), the amount of described azole compounds (Dc) is 2 mass parts to 30 mass parts.
The galvanized steel plain sheet that be formed with film of item 2. as described in item 1, in the coating of wherein said galvanized steel plain sheet, Zn content is more than 10 quality %.
3. galvanized steel plain sheets being formed with film as described in item 1 or item 2, at least one material of the epoxy resin that the film formative resin (A) of wherein said hydroxyl is the mylar and hydroxyl that are selected from hydroxyl.
4. galvanized steel plain sheets being formed with film as described in item 3, the mylar that the film formative resin (A) of the hydroxyl in wherein said coating composition (II) is hydroxyl.
The galvanized steel plain sheet that be formed with film of item 5. as described in item 1 to item 4, wherein said crosslinking agent (B) is for being selected from least one crosslinking agent of amino resins, phenolic resins and polyisocyanate compounds, and described polyisocyanate compounds can be end-blocking.
The galvanized steel plain sheet that be formed with film of item 6. as described in item 1 to item 5, wherein said rust resisting pigment (C) is following combination:
(1) at least one vfanadium compound of vanadic anhydride, calcium vanadate, ammonium metavanadate and vanadic acid magnesium is selected from;
(2) silicon-containing compound; And
(3) based on the slaine of phosphoric acid.
7. galvanized steel plain sheets being formed with film as described in item 6, the wherein said slaine based on phosphoric acid (3) for be selected from calcium phosphate, calcium monohydrogen phosphate, calcium dihydrogen phosphate and wherein metallic element be at least one material of the tripolyphosphate slaine of magnesium, aluminium, zinc or calcium.
The galvanized steel plain sheet that be formed with film of item 8. as described in item 1 to item 7, wherein, when adding described compound (Da) of 1 mass parts in the sodium-chloride water solution to the concentration of 100 mass parts being 5 quality % under 25 ° of C, stir the mixture under 25 ° of C 6 hours, under 25 ° of C, make gains leave standstill 24 hours, and filtering supernatant, the pH of gained filtrate is 10 to 13.
The galvanized steel plain sheet that be formed with film of item 9. as described in item 1 to item 8, wherein in described resin (Db), in molecular weight distribution, molecular weight is the mass fraction of the component of 1, less than 000 is 5 quality % to 30 quality %.
The galvanized steel plain sheet that be formed with film of item 10. as described in item 1 to item 9, wherein, when adding described resin (Db) of 1 mass parts in the sodium-chloride water solution to the concentration of 100 mass parts being 5 quality % under 25 ° of C, stir the mixture under 25 ° of C 6 hours, under 25 ° of C, make gains leave standstill 24 hours, and filtering supernatant, the pH of gained filtrate is 3 to 7.
The galvanized steel plain sheet that be formed with film of item 11. as described in item 1 to item 10, wherein said azole compounds (Dc) is for having the azole compounds of triazole group or thiadiazoles group.
The galvanized steel plain sheet that be formed with film of item 12. as described in item 1 to item 11, wherein said coating composition (I) also comprises at least one pigment being selected from titanium dioxide and extender pigment.
The galvanized steel plain sheet that be formed with film of item 13. as described in item 1 to item 12, wherein said coating composition (II) also comprises at least one pigment of rust resisting pigment, titanium dioxide and the extender pigment be selected from except described compound (Da).
The galvanized steel plain sheet that be formed with film of item 14. as described in item 6 or item 7, wherein, the bottom in the described front used toward the outer side is formed the coating be made up of described coating composition (I), and in the superiors at the back side of opposition side, forms the coating be made up of described coating composition (II).
The galvanized steel plain sheet that be formed with film of item 15. as described in item 14, on the bottom of front and back, wherein all form the coating be made up of described coating composition (I), and in the superiors at the described back side used towards inner side, form the coating be made up of described coating composition (II).
Item 16. forms multilayer film and on the back side of described galvanized steel plain sheet, forms the method for one or more layers film on the front of galvanized steel plain sheet, and described method comprises the following steps:
Following coating composition (I) is coated with on the bottom of at least one be contained in the front and back of described galvanized steel plain sheet;
Solidify the film obtained by coating composition described in application (I);
Following coating composition (II) is coated with in the superiors of at least one be contained in described front and back; And
Solidify the film obtained by coating composition described in application (II);
coating composition (I): be the coating composition comprising the film formative resin (A) of hydroxyl, crosslinking agent (B) and rust resisting pigment (C), wherein, based on the described resin (A) of 100 mass parts and the total solids content of described crosslinking agent (B), the amount of described rust resisting pigment (C) is 10 mass parts to 150 mass parts; And
coating composition (II): be comprise the film formative resin (A) of hydroxyl and the coating composition of crosslinking agent (B); Wherein
Described coating composition (II) also comprises at least one compound (Da) being selected from metal silicate and metal ion exchanged silica, and, based on the described resin (A) of 100 mass parts and the total solids content of described crosslinking agent (B), the amount of described compound (Da) is 3 mass parts to 50 mass parts; Or,
Described coating composition (II) also comprises at least one resin (Db) of the film formative resin of film formative resin and the phosphate-containing group being selected from phosphoric acid group, and, based on the described resin (A) of 100 mass parts and the total solids content of described crosslinking agent (B), the amount of described resin (Db) is 5 mass parts to 30 mass parts; Or,
Described coating composition (II) also comprises azole compounds (Dc), and based on the described resin (A) of 100 mass parts and the total solids content of described crosslinking agent (B), the amount of described azole compounds (Dc) is 2 mass parts to 30 mass parts.
The beneficial effect of the invention
The galvanized steel plain sheet being formed with film of the present invention has the film be made up of non-chromium coatings composition formed on two faces of galvanized steel plain sheet, and it is favourable in environmental sanitation.This plate has and forms the effect of film, and this film not only has excellent corrosion resistance in planar portions, and has excellent resistance to white rust in processing department and end face portion, and this is especially can be observable at the use initial stage.Be difficult to realize such resistance to white rust by the anticorrosive coating composition of non-chromium.
Be formed in the galvanized steel plain sheet of film of the present invention, the anticorrosion ability of the coating formed on the bottom of at least one of front and back by using the coating composition (I) comprising rust resisting pigment realizes the corrosion resistance in planar portions; And the rust-proof effect of the coating formed in the superiors of at least one of front and back by using coating composition (II) realizes the resistance to white rust in processing department and end face portion, and described coating composition (II) comprises at least one compound being selected from metal silicate and metal ion exchanged silica.
Because zinc in coating (ion) is converted into zinc oxide and produces the white rust in galvanized steel plain sheet.White rust is the state caused by the bulk zinc oxide formed on galvanizing surface, and its color is the white that white or part comprise khaki spot.The outward appearance picture of white rust sticks to the pale powder on surface.Particularly when coating be exposed to wherein coating to be got wet by rainwater, dew etc. and to be not easy in the environment done time, or when coating by rainwater or dew heterogeneity get wet time, white rust may occur.Due to this reason, white rust more may occur in processing department and end face portion.Because white rust is bulk zinc oxide, so even slight radiation looks like serious corrosion and is very visible.
Be formed in the galvanized steel plain sheet of film of the present invention, use comprise aforesaid component (Da), the coating composition (II) of (Db) and/or (Dc) forms coating in the superiors of at least one of front and back.Before the zinc oxide formation causing white rust, the phosphate group of the film formative resin of the silicate ion of the zinc ion produced in processing department and end face portion and metal silicate and metal ion exchanged silica, the film formative resin of phosphoric acid group and/or phosphate-containing group and/or phosphate group, and/or azole compounds reaction.Thus, effectively catch zinc ion, therefore, it is possible to suppress the formation of zinc oxide.Therefore, the galvanized steel plain sheet being formed with film of the present invention has resistance to white rust excellent significantly in processing department and end face portion.
Embodiment describes
The galvanized steel plain sheet being formed with film of the present invention has multilayer film on the front face and has one or more layers film on the back side, on the bottom of at least one of front and back, wherein form the coating be made up of coating composition (I), described coating composition (I) comprises the film formative resin (A) of hydroxyl, crosslinking agent (B) and rust resisting pigment (C), and in the superiors of at least one of front and back, form the coating be made up of coating composition (II), described coating composition (II) comprises the film formative resin (A) of hydroxyl, crosslinking agent (B) and metal silicate and/or metal ion exchanged silica (Da), the film formative resin of phosphoric acid group and/or the film formative resin (Db) of phosphate-containing group, and/or azole compounds (Dc).
The galvanized steel plain sheet (hereafter also referred to as " plated steel sheet of the present invention ") being formed with film of the present invention is described below in detail.
coating composition (I)
Coating composition (I) comprises the film formative resin (A) of hydroxyl, crosslinking agent (B) and rust resisting pigment (C).
the film formative resin (A) of hydroxyl
As the film formative resin of the hydroxyl for coating composition (I), the resin of any hydroxyl can be used without limitation, as long as they are generally used for coating composition field and have the ability forming film.Its representative instance comprises the mixture of the resin of one or more hydroxyls, such as mylar, epoxy resin, acrylic resin, fluororesin and vinyl chloride resin.Especially, at least one organic resin be selected from the mylar of hydroxyl and the epoxy resin of hydroxyl can be suitable for use as described film formative resin.
The example of the mylar of hydroxyl comprises the modified product of oil-free polyester resin, oil-modified alkyd resin and these resins, alkyd resins, epoxide modified mylar and acrylic acid modified mylar that the mylar that such as ammonia is ester modified, ammonia are ester modified.The mylar of preferred hydroxyl is number-average molecular weight is 1,500 to 35,000, and is preferably 2,000 to 25,000; Glass transition temperature (Tg) is 10 ° of C to 100 ° of C, and is preferably 20 ° of C to 80 ° of C; And hydroxyl value is 2mgKOH/g to 100mgKOH/g, and be preferably the mylar of those hydroxyls of 5mgKOH/g to 80mgKOH/g.
In this specification, based on the retention time (retention volume) with the polystyrene standard of known molecular amount measured under the same conditions, determine number-average molecular weight and weight average molecular weight by the retention time measured by gel permeation chromatography (GPC) (retention volume) is converted into polystyrene molecular weight.
Such as, more specifically, by being used as " HLC-8120GPC " of gel permeation chromatograph (being produced by Tosoh Corporation); Four posts, i.e. " TSKgelG4000HXL " post, two " TSKgel G3000HXL " posts and " TSKgel G2000HXL " post (being produced by Tosoh Corporation); And as the differential refractometer detector of detector; Measure number-average molecular weight and weight average molecular weight under the following conditions: mobile phase: oxolane, measuring tempeature: 40 ° of C, flow velocity: 1mL/min.In this specification, the glass transition temperature (Tg) of resin is measured by differential scanning calorimeter (DSC).
Oil-free polyester resin is the esterification products of polyacid component and polyol component.The polyacid component of main use is such as one or more binary acid, and it is selected from phthalic anhydride, M-phthalic acid, terephthalic acid (TPA), tetrabydrophthalic anhydride, hexahydrophthalic anhydride, butanedioic acid, fumaric acid, adipic acid, decanedioic acid, maleic anhydride etc.; And the esterification products of the low alkyl group of these acid.If needed, monoacid can be used in combination, such as benzoic acid, crotonic acid and p-tert-butyl benzoic acid; Ternary acid or more senior polyacid, such as trimellitic anhydride, methylcyclohexene tricarboxylic acids and pyromellitic acid anhydride; Deng.These polyacids can be used separately or with the form of two or more combinations.Especially preferred acid constituents is the low alkyl group esterification product of M-phthalic acid, terephthalic acid (TPA) and these acid.The polyol component of main use is such as, dihydroxylic alcohols, such as ethylene glycol, diethylene glycol, propane diols, BDO, neopentyl glycol, 3-methyl pentanediol, Isosorbide-5-Nitrae-hexylene glycol and 1,6-hexylene glycol.In addition, if needed, ternary or more senior polyalcohol can be used in combination, such as glycerine, trimethylolethane, trimethylolpropane and pentaerythrite.These polyalcohols can be used separately or with two or more combining forms.Esterification or the ester exchange reaction of two kinds of components can be carried out by known method.
Except the acid constituents of above-mentioned oil-free polyester resin and alkoxide component, also make fatty acid oil react by known method and obtain alkyd resins.The example of fatty acid oil comprises coco-nut oil fatty acid, soya fatty acid, linseed oil aliphatic acid, safflower oil fatty acid, ready denier oil acid, dehydrated castor oil fatty acid, tung oil fatty acid etc.The oily length of alkyd resins is preferably less than 30%, and is especially preferably about 5% to 20%.
The example of the mylar that ammonia is ester modified comprises the ester modified mylar of those ammonia of making polyisocyanate compounds and above-mentioned oil-free polyester resin react or react with low-molecular-weight oil-free polyester resin and obtain by known method, obtains this low-molecular-weight oil-free polyester resin by making the acid constituents that uses in the preparation of above-mentioned oil-free polyester resin and alkoxide component reaction.The ester modified alkyd resins of such ammonia comprises the ester modified alkyd resins of those ammonia of making polyisocyanate compounds and above-mentioned alkyd resins react or react with low-molecular-weight alkyd resins and obtain by known method, by making the component reaction that uses in the preparation of above-mentioned alkyd resins and obtaining this low-molecular-weight alkyd resins.The example that can be used in preparing the polyisocyanate compounds of the ester modified mylar of ammonia and the ester modified alkyd resins of ammonia comprises hexamethylene diisocyanate, IPDI, XDI, toluene di-isocyanate(TDI), 4,4 '-methyl diphenylene diisocyanate, 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), 2,4,6-tri-TI (2,4,6-triisocyanatotoluene) etc.The ester modified resin of suitable ammonia is generally wherein ester modified relative to ammonia resin, and modification degree makes the amount of the polyisocyanate compounds forming the ester modified resin of this ammonia be the ester modified resins of those ammonia of below 30wt.%.
The example of epoxide modified mylar comprises by using by the mylar obtained in the component used during the above-mentioned mylar of preparation, and the product making the carboxyl of resin and obtain containing the resin reaction of epoxy; By polyisocyanate compounds, the hydroxyl of mylar is connected with the hydroxyl of epoxy resin and the product obtained; And other product to be obtained by the reaction (such as, addition, condensation or grafting) of mylar and epoxy resin.The modification degree of epoxide modified mylar makes relative to epoxide modified mylar usually, and the amount of epoxy resin is preferably 0.1wt.% to 30wt.%.
The example of acrylic acid modified mylar comprises by using by the mylar obtained in the component used during the above-mentioned mylar of preparation, and makes the carboxyl of resin or hydroxyl and contain the reactive acrylic resin with these groups with groups such as reactive such as carboxyl, hydroxyl or epoxy radicals and the product obtained; Use the product that polymerization initiator is obtained by (methyl) acrylic acid, (methyl) acrylate etc. and the glycerol polymerization of mylar; Deng.The modification degree of acrylic acid modified mylar makes relative to acrylic acid modified mylar usually, and the amount of acrylic resin is preferably 0.1wt.% to 50wt.%.
In above-mentioned mylar, in the balance of processability, corrosion resistance etc., oil-free polyester resin and epoxide modified mylar are especially preferred.
The example being suitable for use as the epoxy resin of the film formative resin of hydroxyl comprises bisphenol-type epoxy resin, phenol aldehyde type epoxy resin and the epoxy resin by the modification that makes the epoxide group of these epoxy resin or hydroxyl and multiple modifier react and obtain.In the preparation of the epoxy resin of modification, the opportunity of being carried out modification by modifier is not particularly limited.The mid-term can prepared at epoxy resin or latter stage carry out modification.
Available bisphenol-type epoxy resin can be by optionally at catalyst (such as, base catalyst) existence under, by those bisphenol-type epoxy resins making chloropropylene oxide and bisphenol compound condensation increase molecular weight and obtain, or be by optionally at catalyst (such as, base catalyst) existence under, by making chloropropylene oxide and bisphenol compound condensation provide low-molecular-weight epoxy resin, then make those bisphenol-type epoxy resins that this low-molecular-weight epoxy resin and bis-phenol polyaddition obtain.
The example of bisphenol compound comprises two (4-hydroxy phenyl) methane [Bisphenol F], 1, two (4-hydroxy phenyl) ethane of 1-, 2, two (4-hydroxy phenyl) propane [bisphenol-A] of 2-, 2, two (4-hydroxy phenyl) butane [bisphenol b] of 2-, two (4-hydroxy phenyl)-1, 1-iso-butane, two (4-hydroxy-tert-butyl-phenyl)-2, 2-propane, p-(4-hydroxy phenyl) phenol, oxygen base two (4-hydroxy phenyl), sulfonyl two (4-hydroxy phenyl), 4, 4 '-dihydroxy benaophenonel, two (2 hydroxy naphthalene base) methane etc.Wherein, bisphenol-A and Bisphenol F are suitable for using.These bis-phenols can be used separately or with two or more combining forms.
The commercial products of bisphenol-type epoxy resin comprises, such as Epikote 828, Epikote 812, Epikote 815, Epikote 820, Epikote 834, Epikote 1001, Epikote 1004, Epikote 1007, Epikote 1009 and Epikote 1010 (being produced by Japanese Epoxy Resin Co., Ltd.); Araldite AER6099 (being produced by Asahi-Ciba Ltd.); Epomix R-309 (being produced by Mitsui Chemicals, Inc.); Deng.
The example being suitable for use as the phenol aldehyde type epoxy resin of the film formative resin of hydroxyl comprises phenol novolak type epoxy, cresol novolak type epoxy resin, the phenol glyoxal type epoxy resin in the molecule with many epoxide groups and other phenol aldehyde type epoxy resin multiple.
The example of modified epoxy comprises the epoxy ester resin obtained by the reaction of above-mentioned bisphenol-type epoxy resin or phenol aldehyde type epoxy resin and drying oil fatty acid; The Epocryl obtained by the reaction of above-mentioned bisphenol-type epoxy resin or phenol aldehyde type epoxy resin and the polymerizable unsaturated monomer component containing acrylic or methacrylic acid; The epoxy resin that the ammonia obtained by the reaction of above-mentioned bisphenol-type epoxy resin or phenol aldehyde type epoxy resin and isocyanate compound is ester modified; And by the epoxide group of above-mentioned bisphenol-type epoxy resin, phenol aldehyde type epoxy resin or modified epoxy and the reaction of amines to introduce amino or quaternary ammonium salt and the epoxy resin of the amine modification obtained.
crosslinking agent (B)
Crosslinking agent (B) reacts to form the film solidified with the film formative resin (A) of hydroxyl.Arbitrary crosslinking agent can be used without limitation, react with cured resin with the film formative resin (A) of hydroxyl as long as they can be waited by heating.Especially, amino resins, phenolic resins and can be able to be suitable for using for the polyisocyanate compounds of end-blocking.These crosslinking agents can be used separately or with the form of two or more combinations.
The example of amino resins comprises the methylolated amino resins obtained by the reaction of aldehyde and amino group, and described amino group is melamine, urea, benzoguanamine, acetylguanamine, steroguanamine, spiral shell guanamines or dicyandiamide such as.The example that can be used in the aldehyde of above-mentioned reaction comprises formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde etc.In addition, also can use by the etherificate of above-mentioned methylolated amino resins and suitable alcohol and the amino resins obtained.The example that can be used in the alcohol of etherificate comprises methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, 2-ethyl butanol, 2-Ethylhexyl Alcohol etc.
Cross-linking reaction can be there is as the phenolic resins of crosslinking agent and the film formative resin (A) of hydroxyl.The example comprises by heating phenol component in the presence of a catalyst and formaldehydes introduces methylol to carry out condensation reaction, and makes the part or all of methylol of the methylolated phenolic resins of gained and alcohol carry out alkyl etherified and first rank phenolic aldehyde (resol) type phenolic resins that is that obtain.
In the preparation of first rank novolac type phenolic resin, difunctional phenol compound, trifunctional oxybenzene compound, four senses or higher functional oxybenzene compound etc. can be used as initial phenol component.
For such phenol compound, the example of difunctional phenol compound comprises orthoresol, paracresol, p-tert-butylphenol, p-ethyl-phenol, 2,3-xylenols, 2,5-xylenols etc.The example of trifunctional oxybenzene compound comprises carbolic acid, metacresol, m-ethyl-phenol, 3,5-xylenols, m-metoxyphenol etc.The example of four trifunctional phenol compounds comprises bisphenol-A, Bisphenol F etc.Wherein, in improvement resistance to marring, preferred trifunctional or higher functional oxybenzene compound, especially carbolic acid and/or metacresol.These phenol compounds can be used separately or with the form of two or more combinations.
The example that can be used in the formaldehydes preparing phenolic resins comprises formaldehyde, paraformaldehyde, trioxane etc.These formaldehydes can be used separately or with the form of two or more combinations.
It is the monohydric alcohol with 1 to 8 carbon atom, preferably 1 to 4 carbon atom that the part methylol of described methylolated phenolic resins can be made to carry out alkyl etherified suitable alcohol.Suitable monohydric alcohol is methyl alcohol, ethanol, normal propyl alcohol, n-butanol, isobutanol etc.
With regard to the aspect such as reactivity of the film formative resin (A) of they and hydroxyl, suitable phenolic resins is that each benzene nucleus has average more than 0.5, preferably 0.6 to 3.0 alkoxy methyl.
Can be also can being used as in the polyisocyanate compounds of crosslinking agent of end-blocking, the example of the polyisocyanate compounds of non-end-blocking comprises aliphatic diisocyanate, such as hexamethylene diisocyanate and trimethyl hexamethylene diisocyanate; Ring-shaped fat (cyclo) aliphatic diisocyanates, such as hydrogenation of benzene dimethylene diisocyanate and IPDI; Aromatic diisocyanate, such as toluene di-isocyanate(TDI), XDI, 4,4 '-methyl diphenylene diisocyanate and rough MDI; And other organic diisocyanate.Available example also comprises the adduct of such organic diisocyanate and polyalcohol, low molecular weight polyester resin, water etc.; The cyclopolymer of such organic diisocyanate; Isocyanates biuret form adduct etc.
By the free isocyanate groups of above-mentioned polyisocyanate compounds group's end-blocking being obtained with end-capping reagent the polyisocyanate compounds of end-blocking.The example of end-capping reagent comprises the end-capping reagent based on phenol, such as phenol, cresols and xylenols; Based on the end-capping reagent of lactams, such as epsilon-caprolactams, δ-valerolactam and butyrolactam; Based on the end-capping reagent of alcohol, such as methyl alcohol, ethanol, n-butanol, isobutanol or the tert-butyl alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether and benzylalcohol; Based on the end-capping reagent of oxime, such as formamidoxime, acetyl oxime, acetoxime, methyl ethyl ketone oxime, diacetyl monooxime, diphenyl-ketoxime and cyclohexanone oxime; Based on the end-capping reagent of active methylene group, such as dimethyl malenate, diethyl malonate, ethyl acetoacetate and acetylacetone,2,4-pentanedione; And other end-capping reagent.The free isocyanate groups group of the above-mentioned polyisocyanate compounds of easy end-blocking can be come by mixing polyisocyanate compounds and above-mentioned end-capping reagent.
With regard to corrosion resistance, boiling water resistance, processability, curability etc., the film formative resin (A) of hydroxyl and the ratio of crosslinking agent (B) are preferably as follows: based on the component (A) of 100 mass parts and the total solids content of (B), the amount of the film formative resin (A) of hydroxyl is 55 mass parts to 95 mass parts, and is preferably 60 mass parts to 95 mass parts; And the amount of crosslinking agent (B) is 5 mass parts to 45 mass parts, and be preferably 5 mass parts to 40 mass parts.
If needed, curing catalysts can be added to improve the curability of coating composition (I).When crosslinking agent (B) is for amino resins, during the melmac of the etherificate of especially low-molecular-weight methyl etherified melmac or methyl ether-butyl ether mixing, the sulfoacid compound of sulfoacid compound or amine-neutralization can be suitable for use as curing catalysts.The representative instance of sulfoacid compound comprises p-methyl benzenesulfonic acid, DBSA, dinonylnaphthalene sulfonic acid, dinonylnaphthalene disulfonic acid etc.The amine of the sulfoacid compound of amine neutralization can be arbitrary primary amine, swollen amine and tertiary amine.Wherein, with regard to the aspect such as physical property of the stability of coating composition, reaction facilitation effect, gained film, the p-methyl benzenesulfonic acid of amine neutralization and/or the DBSA of amine neutralization are preferred.
When crosslinking agent (B) is for phenolic resins, the sulfoacid compound of above-mentioned sulfoacid compound or amine neutralization can be suitable for use as curing catalysts.
When the polyisocyanate compounds that crosslinking agent (B) is end-blocking, suitable curing catalysts is those curing catalysts promoting that end-capping reagent dissociates.Such as, preferred curing catalysts is organo-metallic catalyst, and such as tin octoate, two (2 ethyl hexanoic acid) dibutyl tin, two (2 ethyl hexanoic acid) dioctyl tin, dioctyl tin diacetate, dibutyl tin laurate, dibutyltin oxide, di-n-octyltin oxide and 2 ethyl hexanoic acid are plumbous.
When the mixture that crosslinking agent (B) is two or more crosslinking agent, can use in combination the effective curing catalysts of each crosslinking agent.
rust resisting pigment (C)
As rust resisting pigment (C), chromium pigment and non-chromium pigment can both use, as long as they have corrosion resistance.With regard to human health and environmental protection, non-chromium rust resisting pigment is preferred.
The example of chromium rust resisting pigment comprises strontium chromate, zinc chromate, potassium chromate zinc, barium chromate, chromic anhybride, chromic acid chromium, chromium phosphate etc.
The example of non-chromium rust resisting pigment comprises vfanadium compound, such as vanadic anhydride, calcium vanadate, ammonium metavanadate and vanadic acid phosphorus; Silicon-containing compound, such as metal silicate and silica dioxide granule; Based on the slaine of phosphoric acid, such as trbasic zinc phosphate, aluminum phosphate, calcium phosphate, magnesium monohydrogen phosphate and aluminium triphosphate; The calcining mixt etc. of the calcining mixt of zinc molybdate, manganese oxide and vanadium oxide, calcium phosphate and vanadium oxide.These rust resisting pigments can be used separately or with the form of two or more combinations.
Especially, following vfanadium compound (1), silicon-containing compound (2) and the mixture based on the slaine (3) of phosphoric acid can be suitable for use as the rust resisting pigment (C) in coating composition (I).
vfanadium compound (1)
Vfanadium compound (1) is for being selected from least one vfanadium compound of vanadic anhydride, calcium vanadate, ammonium metavanadate and vanadic acid magnesium.Vanadic anhydride, calcium vanadate, ammonium metavanadate and vanadic acid magnesium have excellent pentavalent vanadium ion stripping property in water.The pentavalent vanadium ion of release from vfanadium compound (1) with react with thus effectively for improvement of corrosion resistance from the metal of other rust resisting pigment or ionic material.
silicon-containing compound (2)
Silicon-containing compound (2) is for being selected from least one of metal silicate and silica dioxide granule.Metal silicate is the salt of silica and metal oxide, and can use arbitrary orthosilicate, polysilicate etc.The example of silicate comprises calcium silicates, magnesium silicate, zinc silicate, alumina silicate, orthosilicic acid aluminium, aluminium hydrosilicate, calcium aluminosilicate, lagoriolite, alumina silicate beryllium, sodium metasilicate, calcium orthosilicate, calcium metasilicate, calcium silicates sodium, zirconium silicate, magnesium orthosilicate, metasilicic acid magnesium, calcium magnesium silicate, manganous silicate, barium silicate, olivine, garnet, thortveitite, smithsonite, benitoite, carlosite, greenstone, diopside, wollastonite, rhodonite, the tremolite, eakleite, talcum, fish-eye stone, aluminosilicate, borosilicate, beryllosilicate, feldspar, zeolite etc.Wherein, calcium silicates, calcium orthosilicate and calcium metasilicate are preferred as metal silicate.
For silica dioxide granule, arbitrary silica dioxide granule can be used without any restriction.The example comprises surperficial untreated SiO 2 powder, the surface SiO 2 powder of organic matter process, calcium ion-exchanged silica dioxide granule, organic solvent dispersion colloidal silica etc.
The example of the silica dioxide granule of the untreated or surface organic matter process in surface comprises SiO 2 powder, and its average grain diameter is 0.5 μm to 15 μm, is more preferably 1 μm to 10 μm, and organic solvent dispersion colloidal silica.Suitable SiO 2 powder is that oil absorption is 30ml/100g to 350ml/100g and is preferably those SiO 2 powders of 30ml/100g to 150ml/100g.Its commercially available product comprises Sylicia 710, Sylicia 740, Sylicia 550 and Aerosil R972 (being produced by Fuji Sylicia Chemical, Ltd.); Mizukasil P-73 (being produced by Mizusawa Industrial Chemicals, Ltd.); Gasil200DF (being produced by Crosfield Ltd.) etc.
Calcium ion-exchanged silica is the silica dioxide granule by ion-exchange, calcium ion being incorporated to nanoporous silica silicon carrier and obtaining.The commercially available product of calcium ion-exchanged silica comprises SHIELDEX (registration mark) C303, SHIELDEX AC-3 and SHIELDEX AC-5 (being produced by W.R.Grace & Co.).The calcium ion discharged from calcium ion-exchanged silica participates in electrochemical action and multiple salification, and effectively for improvement of corrosion resistance.In addition, fixing in film silica suppresses the stripping of film under corrosive environment effectively.
Organic solvent dispersion colloidal silica is also referred to as Organic silica sols, and it is by being that the silica dioxide granule of about 5nm to 120nm is stably dispersed in the organic solvent of such as alcohol, ethylene glycol and ether and obtains by particle diameter.Its commercially available product comprises OSCAL series (by Catalysts and Chemicals Ind., Co., Ltd. produces), ORGANO SILICA SOL (being produced by Nissan Chemical Industries, Ltd.) etc.Wherein, calcium ion-exchanged silica dioxide granule is specially suitable.
Above-mentioned silicon-containing compound (2) can be used separately or with the form of two or more combinations.
based on the slaine (3) of phosphoric acid
Slaine (3) based on phosphoric acid is selected from least one in phosphate metal salt, phosphoric acid hydrogen slaine and tripolyphosphate slaine.Metal based on the slaine of phosphoric acid is not particularly limited.Suitable metal is Ca, Zn, Al and Mg.Wherein, Ca is specially suitable.
Example based on the slaine of phosphoric acid comprises calcium phosphate, ammonium calcium phosphate, calcium monohydrogen phosphate, calcium dihydrogen phosphate, calcium phosphate fluoride, trbasic zinc phosphate, aluminum phosphate, magnesium phosphate, di(2-ethylhexyl)phosphate magnesium, phosphoric acid hydrogen zinc, aluminum phosphate, magnesium phosphate, phosphoric acid hydrogen aluminium, magnesium monohydrogen phosphate and ammonium magnesium phosphate; Aluminium triphosphate, aluminium dihydrogen tripolyphosphate and wherein metallic element be other tripolyphosphate slaine of magnesium, aluminium, zinc or calcium.Wherein, with regard to corrosion resistance, calcium phosphate, calcium monohydrogen phosphate, calcium dihydrogen phosphate and wherein metallic element is the tripolyphosphate slaine of magnesium, aluminium, zinc or calcium is particularly preferred.The phosphate ion discharged from the slaine (3) based on phosphoric acid and the metal ion of such as Ca, Zn, Al and Mg improve efficiently corrosion resistance.
With regard to corrosion resistance, based on the film formative resin (A) of the hydroxyl of 100 mass parts and the total solids content of crosslinking agent (B), in coating composition (I), the amount of rust resisting pigment (C) is preferably 10 mass parts to 150 mass parts, and is more preferably 15 mass parts to 90 mass parts.Especially, with regard to corrosion resistance, as rust resisting pigment (C), vfanadium compound (1), silicon-containing compound (2) and based on the ratio of the slaine (3) of phosphoric acid preferably in following scope:
Vfanadium compound (1): 3 mass parts to 50 mass parts, and be preferably 5 mass parts to 30 mass parts;
Silicon-containing compound (2): 3 mass parts to 50 mass parts, and be preferably 5 mass parts to 30 mass parts; And
Slaine (3) based on phosphoric acid: 3 mass parts to 50 mass parts and be preferably 5 mass parts to 30 mass parts.
Can the rust resisting pigment (C) in coating composition (I) be used as by the said components (1) of mixing specified quantitative, (2) and (3) and work in coordination with improvement corrosion resistance.
In addition, using the component (1) of specified quantitative, (2) and the mixture of (3) as rust resisting pigment (C) when, with regard to component (1), and (3) solubility in water (2), with the reactivity of rust resisting pigment solution and metal-plated plate, when under 25 ° of C by the component (1) of 1 mass parts of the amount (mass parts) in its quantification range, (2) and the mixture of (3) concentration that joins 100 mass parts is in the sodium-chloride water solution of 5 quality % time, stir the mixture under 25 ° of C 6 hours, under 25 ° of C, make gains leave standstill 48 hours, and filtering supernatant, the pH of gained filtrate is preferably 3 to 10, and be more preferably 5 to 9.With regard to corrosion resistance, the pH within the scope of this is preferred.
Except the film formative resin (A) of hydroxyl, crosslinking agent (B), rust resisting pigment (C) and the optional curing catalysts added, if needed, coating composition (I) also can comprise coloring pigment, extender pigment, ultra-violet absorber, ultra-violet stabilizer, organic solvent; Sagging inhibitor, defoamer, painting face controlling agent and can be used in other additive in coating composition field.The form of coating composition (I) can be any one of organic solvent type coatings composition, water-based paint compositions and powder paint compositions.
The example of coloring pigment comprises organic coloring pigments, such as the organic red pigment of phthalocyanine blue, phthalocyanine green and the type such as azo, quinacridone; And inorganic colored pigments, such as titanium white, titan yellow, red iron oxide, carbon black and multiple calcined pigment.Wherein, titanium white can suitable use.
The example of extender pigment comprises talcum, clay, silica, mica, alumina, calcium carbonate, barium sulfate etc.
The example of ultra-violet absorber comprises benzotriazole cpd, such as 2-(2-hydroxyl-3, 5-bis--t-amyl group phenyl)-2H-BTA, iso-octyl-3-(3-(2H-BTA-2-base)-5-tert-butyl-hydroxy phenyl propionic ester), 2-[2-hydroxyl-3, 5-bis-(1, 1-dimethyl benzene) phenyl]-2H-BTA, 2-[2-hydroxyl-3-dimethyl benzyl-5-(1, 1, 3, 3-tetramethyl butyl) phenyl] condensation product of-2H-BTA and methyl-3-[the 3-tert-butyl group-5-(2H-BTA-2-base)-4-hydroxy phenyl] propionic ester and Liquid Macrogol, triaizine compounds, such as two (2,4-the 3,5-dimethylphenyl)-1,3,5-triazines of 2-[4-(2-hydroxyl-3-dodecyl oxygen base propyl group) oxygen base]-2-hydroxy phenyl-4,6-, oxalic acid anilides, such as oxalamide-N-(2-ethoxyl phenenyl)-N'-(2-ethylphenyl)-(oxamides) and oxalamide-N-(2-ethoxyl phenenyl)-N'-(4-Permethyl 99A base phenyl)-(oxamides), Deng.
The example of ultra-violet stabilizer comprises hindered amine compound and hindered phenol compound; CHIMASSORB 944, TINUVIN 144, TINUVIN 292, TINUVIN 770, IRGANOX 1010 and IRGANOX 1098 (trade (brand) name; Produced by Ciba SpecialtyChemicals); Deng.
Ultra-violet absorber and/or ultra-violet stabilizer are joined in coating composition, prevents the surface deterioration of the film formed by coating composition (I) caused by the photoconduction arrived in film coated surface.Therefore, it is possible to prevent the stripping between the film that formed by coating composition (I) and upper coating film, and excellent corrosion resistance can be kept.
If needed, the above-mentioned organic solvent that mixing can mix with coating composition (I) is to improve the coating easness etc. of coating composition (I).Organic solvents available is to dissolve or to disperse the film formative resin (A) of hydroxyl and those organic solvents of crosslinking agent (B).Its instantiation comprises the solvent based on hydrocarbon, such as toluene, dimethylbenzene and high point petroleum hydrocarbon; Based on the solvent of ketone, such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone and isophorone; Based on the solvent of ester, such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate and diethylene glycol ether acetate alone; Based on the solvent of alcohol, such as methyl alcohol, ethanol, isopropyl alcohol and butanols; Based on the solvent of ether alcohol, such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether and diethylene glycol monobutyl ether etc.These solvents can be used separately or with the form of two or more combinations.
With regard to the aspect such as corrosion resistance, acid resistance, processability of film, the glass transition temperature of the cured coating film using coating composition (I) to obtain is preferably 40 ° of C to 115 ° of C, and is more preferably 50 ° of C to 105 ° of C.In this specification, the glass transition temperature of film is for using automation dynamic viscoelastometer (Dynamic Viscoelastometer Model VibronDDV-IIEA, used by Toyo Baldwin Co., Ltd.) in temperature dispersion is measured, change by tan δ the maximum temperature determined with the frequency of 110Hz.
When the rust resisting pigment (C) in coating composition (I) be vfanadium compound (1), silicon-containing compound (2) and the mixture based on the slaine (3) of phosphoric acid time, by there is excellent corrosion resistance to galvanized steel plain sheet coating coating composition (I) film that formed.The present inventor thinks that its reason is as follows: such as, because of the metal ion that produced by the chlorion dissolved material metal in corrosive environment and pentavalent vanadium ion (vanadic acid ion, VO 3 -and VO 4 3-) directly produce precipitable salt without the need to redox; And because effectively forming precipitable salt or compound, so be effectively coated with the exposure of material by material metal, the trivalent vanadium ion produced through redox by pentavalent vanadium ion and silicate ion.In addition, have adjusted the pH in the region that is just corroded at the phosphate ion of same time stripping, and it is close to the pH scope being particularly suitable for the redox reaction of carrying out pentavalent vanadium ion and material metal.Especially, such as aluminium etc. in the alloy containing low content has in this type galvanized steel plain sheet of the metal of strong passivation, is desirably in the component being carried out easy passivation stripping from rust resisting pigment in the zinc in such as edge part and deep portion and the different metal battery forming portion of iron by film forming.In this, the atmosphere pH that phosphoric acid hydrogen slaine is considered to stablize institute's stripping as brute force to acidic side component and play an important role.In addition, as the component (1) of rust resisting pigment (C), (2) and (3) combinationally use the weakness that effectively can overcome each component (1), the acid resistance of (2) and (3), alkali resistance and resistance to water.Think and achieve excellent corrosion resistance, this is because play great effect based on the synergy of these effects of rust resisting pigment.
coating composition (II)
Coating composition (II) comprises film formative resin (A) and the crosslinking agent (B) of the hydroxyl of special ratios, and also comprises metal silicate and/or metal ion exchanged silica (Da), the film formative resin of phosphoric acid group and/or the film formative resin (Db) of phosphate-containing group and/or azole compounds (Dc).
As the film formative resin of the hydroxyl used in coating composition (II), as coating composition (I), arbitrary hydroxy-containing resin can be used without limitation, as long as they are generally used for coating composition field and have the ability forming film.Its representative instance comprises more than one hydroxy-containing resin mixture, such as mylar, epoxy resin, acrylic resin, fluororesin and vinyl chloride resin.Especially, at least one organic resin be selected from the mylar of hydroxyl and the epoxy resin of hydroxyl is suitable for using.
The example of the mylar of hydroxyl comprises the modified product of oil-free polyester resin, oil-modified alkyd resin and these resins, such as urethane modified polyester resin, the ester modified alkyd resins of ammonia, epoxy modified polyester resin and acrylic acid modified polyester resin.Preferred hydroxyl group containing polyester resin is number-average molecular weight is 2,000 to 20,000, and especially 3,000 to 15,000; Glass transition temperature (Tg) is 0 ° of C to 70 ° of C, and especially 10 ° of C to 50 ° of C; And hydroxyl value is 5mgKOH/g to 80mgKOH/g, and those resins of especially 10mgKOH/g to 50mgKOH/g.
The example of oil-free polyester resin, alkyd resins, urethane modified polyester resin, the ester modified alkyd resins of ammonia, epoxy modified polyester resin and acrylic acid modified polyester resin comprise that the example as the component of coating composition (I) mentions those.In such mylar, with regard to the balance of the aspect such as processability, corrosion resistance, oil-free polyester resin and epoxy modified polyester resin are particularly preferred.
The example being suitable for use as the epoxy resin of the film formative resin of hydroxyl comprises bisphenol-type epoxy resin and phenol aldehyde type epoxy resin; The modified epoxy obtained by the epoxide group of these epoxy resin or the reaction of hydroxyl and multiple modifier; Deng.In the preparation of modified epoxy, the opportunity of being carried out modification by modifier is not particularly limited.Modification can be carried out in the mid-term or latter stage of preparing epoxy resin.
The example of bisphenol-type epoxy resin, phenol aldehyde type epoxy resin and modified epoxy comprise that the example as the component of coating composition (I) mentions those.
crosslinking agent (B)
As coating composition (I), crosslinking agent (B) reacts to form the film solidified with the film formative resin (A) of hydroxyl.They any crosslinking agent can be used without limitation, as long as can be reacted by the film formative resin (A) of the modes such as heating and hydroxyl with cured resin.Especially, amino resins, phenolic resins and can be able to be suitable for using for the polyisocyanate compounds of end-blocking.These crosslinking agents can be used separately or with the form of two or more combinations.
Amino resins, phenolic resins and can be those mentioned by the component example as coating composition (I) of the example of the polyisocyanate compounds of end-blocking.
With regard to corrosion resistance, boiling water resistance, processability, curability etc., the film formative resin (A) of hydroxyl and the ratio of crosslinking agent (B) are preferably as follows: based on the component (A) of 100 mass parts and the total solids content of (B), the amount of the film formative resin (A) of hydroxyl is 50 mass parts to 95 mass parts, and particularly 70 mass parts to 90 mass parts; And the amount of crosslinking agent (B) is 5 mass parts to 50 mass parts, and particularly 10 mass parts to 30 mass parts.
If needed, curing catalysts can be added to improve the curability of coating composition (II).The example of curing catalysts comprises as those mentioned by the component example of coating composition (I).
When the mixture that crosslinking agent (B) is two or more crosslinking agent, can use in combination the effective curing catalysts of each crosslinking agent.
compound (Da)
Compound (Da) is for being selected from least one material in metal silicate and metal ion exchanged silica.
metal silicate
Metal silicate is the salt of silica and metal oxide, and can use arbitrary orthosilicate, polysilicate etc.The example of silicate comprises calcium silicates, magnesium silicate, zinc silicate, alumina silicate, orthosilicic acid aluminium, aluminium hydrosilicate, calcium aluminosilicate, lagoriolite, alumina silicate beryllium, sodium metasilicate, calcium orthosilicate, calcium metasilicate, calcium silicates sodium, zirconium silicate, magnesium orthosilicate, metasilicic acid magnesium, calcium magnesium silicate, manganous silicate, barium silicate, olivine, garnet, thortveitite, smithsonite, benitoite, carlosite, greenstone, diopside, wollastonite, rhodonite, the tremolite, eakleite, talcum, fish-eye stone, aluminosilicate, borosilicate, beryllosilicate, feldspar, zeolite etc.Suitable metal silicate comprises those of calcium or magnesium.These metal silicates can be used separately or with the form of two or more combinations.
metal ion exchanged silica
Metal ion exchanged silica is the silica dioxide granule by ion-exchange, the metal cation of such as calcium ion being joined nanoporous silica silicon carrier and obtain.The example of metal ion exchanged silica comprises calcium ion-exchanged silica, magnesium ion exchanges silica, cobalt ions exchanges silica etc.
It is 0.5 μm to 15 μm that suitable metal ion exchanged silica comprises average grain diameter, be preferably 1 μm to 10 μm, and oil absorption is 30ml/100g to 300ml/100g, and is preferably the fine silica powder of 30ml/100g to 150ml/100g.
Especially, calcium ion-exchanged silica can be suitable for use as metal ion exchanged silica.The commercially available product of calcium ion-exchanged silica comprises SHIELDEX (registration mark) C303, SHIELDEX AC-3, SHIELDEX C-5 (being produced by W.R.Grace & Co.) etc.
Participate in electrochemical action and multiple salification from the metal cation (such as, calcium ion) of metal ion exchanged silica release, and effectively improve corrosion resistance.In addition, effectively improve the resistance to white rust of multilayer film from the silicate ion of metal ion exchanged silica release and suppress to peel off.
The above-mentioned example of metal ion exchanged silica separately or can be used with the form of two or more combinations.
With regard to resistance to white rust, based on the film formative resin (A) of the hydroxyl of 100 mass parts and the total solids content of crosslinking agent (B), in coating composition (II), the amount of compound (Da) is preferably 3 mass parts to 50 mass parts, and is more preferably 5 mass parts to 30 mass parts.When the amount of compound (Da) is more than 50 mass parts, resistance to white rust is tending towards reducing.This may be because use excessive compound (Da) to cause the resistance to water of film to reduce.
In addition, with regard to compound (Da) solubility in water, and the solution of compound (Da) and the reactivity of metallic plate, when adding compound (Da) of 1 mass parts in the sodium-chloride water solution to the concentration of 100 mass parts being 5 quality % under 25 ° of C, stir the mixture under 25 ° of C 6 hours, gains are made to leave standstill 24 hours, and filtering supernatant, the pH of gained filtrate is preferably 10 to 13.With regard to resistance to white rust, the pH within the scope of this is preferred.
the film formative resin of phosphoric acid group and/or the film formative of phosphate-containing group resin (Db)
In the film formative resin (Db) of phosphoric acid (phosphate) group, the film formative resin of phosphoric acid group comprises phosphate group [-OPO (OH) (OR 1)] (wherein R 1for hydrogen, phenyl or C 1-20alkyl, and particularly preferably hydrogen or C 2-10alkyl).Resinous type is not particularly limited, as long as the film formative resin (A) of itself and hydroxyl is compatible with crosslinking agent (B).The example comprises acrylic resin, epoxy resin, mylar etc.
Can, by such as, make the unsaturated monomer of phosphoric acid group and other polymerizable unsaturated monomer copolymerization to obtain the acrylic resin of phosphoric acid group.
The example of the unsaturated monomer of phosphoric acid group comprises (methyl) acryloxyalkyl (C 2-20) phosphate, such as (2-acryloyl-oxyethyl) phosphate, (2-methacryloxyethyl) phosphate, (2-acryloxypropyl) phosphate, (2-methacryloxypropyl) phosphate, 10-acryloxy decylphosphonic acid ester and 10-Methacryloxydecyl phosphate; By to orthophosphoric acid or acid phosphoric acid ester (C 1-20) medium mole add containing epoxy unsaturated monomer (such as, (methyl) glycidyl acrylate) and obtain addition product; Kayamer PM-2 and KayamerPM-21 (trade name of Nippon Kayaku Co., Ltd.); Deng.Herein, the example of acid phosphoric acid ester comprises methyl orthophosphoric acid, butylphosphoric acid ester, phosphoric acid 2-Octyl Nitrite, isodecyl ester, monododecyl phosphte, phosphoric acid isotridecyl ester, phosphoric acid oil base ester, phenyl phosphate etc.
The unsaturated monomer of hydroxyl is comprised with the example of other polymerizable unsaturated monomer forming the acrylic resin of phosphoric acid group, such as (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 4-hydroxybutyl, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ethers and 2-hydroxyethyl allyl ether with the unsaturated monomer copolymerization of phosphoric acid group; Acrylic acid, methacrylic acid; Vinyl aromatic compounds, such as styrene, AMS, vinyltoluene and α-chlorostyrene; The C of acrylic or methacrylic acid 1-24arrcostab or cycloalkyl ester, such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) acrylic acid (just, different, uncle) butyl ester, (methyl) Hexyl 2-propenoate, (methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) n-octyl, (methyl) decyl acrylate, (methyl) lauryl acrylate, (methyl) octadecyl acrylate and (methyl) isobornyl acrylate; Vinylacetate, vinyl chloride, vinyl ethers, acrylonitrile, methacrylonitrile etc.In the present invention, term " (methyl) acrylate " refers to " acrylate or methacrylate ".
Also can by adding to containing in the unsaturated monomer (such as, (methyl) glycidyl acrylate) of epoxide group and the copolymer resin of other polymerizable unsaturated monomer above-mentioned the acrylic resin that phosphate compound obtains phosphoric acid group.Suitable phosphate compound to be added is orthophosphoric acid, acid phosphoric acid ester etc.The example of acid phosphoric acid ester comprises above-mentioned those as acid phosphoric acid ester example.
Can by adding to epoxy resin the epoxy resin that phosphate compound obtains phosphoric acid group.The example adding the epoxy resin of phosphate compound wherein comprises bisphenol-type epoxy resin, phenol aldehyde type epoxy resin, modified epoxy etc. by making the epoxide group of these epoxy resin or hydroxyl and multiple modifier react and obtain.For the type of phosphate compound to be added, also can be used as to be added to containing the phosphate compound in the unsaturated monomer of epoxide group and the copolymer resin of other polymerizable unsaturated monomer example, mention in the explanation of the acrylic resin of phosphoric acid group those.
Can, by such as, the hydroxyl of mylar and phosphate compound be made to react and obtain the mylar of phosphoric acid group.For the type of the phosphate cpd of question response, in the explanation of the acrylic resin of phosphoric acid group, also can be used as phosphate compound example, mention those.
In the film formative resin of phosphoric acid group and the film formative resin (Db) of phosphate-containing group, can react by making the phosphate group metallizing thing of the film formative resin of above-mentioned phosphoric acid group to form the film formative resin that phosphate obtains phosphate-containing group.The example of the metallic compound reacted with above-mentioned phosphate group comprises calcium oxide, magnesia, cobalt oxide, nickel oxide, zinc oxide, cerium oxide, lanthana etc.
The film formative resin of suitable phosphoric acid group and/or the film formative resin of phosphate-containing group are number-average molecular weights is 1,000 to 20,000, and especially 3,000 to 15,000; Glass transition temperature (Tg) is 0 ° of C to 100 ° of C, and especially 20 ° of C to 60 ° of C; Acid number is 20mgKOH/g to 120mgKOH/g, and especially 30mgKOH/g to 100mgKOH/g; And hydroxyl value is 0mgKOH/g to 50mgKOH/g, and those of especially 5mgKOH/g to 30mgKOH/g.
With regard to the film performance of the resistance to white rust (catching the ability of zinc ion) of gained film and such as resistance to water, in the film formative resin of phosphoric acid group or the film formative resin (Db) of phosphate-containing group, with regard to the coexisting of the stripping property of resin Composition and the resistance to water of film, in molecular weight distribution, molecular weight is 1, the mass fraction of the component of less than 000 is preferably 5 quality % to 30 quality %, and is especially preferably 5 quality % to 20 quality %.
Phosphate group or the phosphate group of the film formative resin (Db) of phosphoric acid (phosphate) group not only effectively catch zinc ion, and the attachment-imparting character improved in acid atmosphere and corrosion resistance.
In coating composition (II), with regard to the coexisting of the resistance to water of film and resistance to white rust, based on the film formative resin (A) of the hydroxyl of 100 mass parts and the total solids content of crosslinking agent (B), the solids content of the film formative resin of phosphoric acid group and/or the film formative resin (Db) of phosphate-containing group is preferably 5 mass parts to 30 mass parts, and is especially preferably 10 mass parts to 20 mass parts.
In addition, with regard to the film formative resin of phosphoric acid group and/or film formative resin (Db) solubility in water of phosphate-containing group, and the solution of resin (Db) and the reactivity of metallic plate, when adding the film formative resin (Db) of film formative resin that solids content is the phosphoric acid group of 1 mass parts and/or phosphate-containing group in the sodium-chloride water solution to the concentration of 100 mass parts being 5 quality % under 25 ° of C, stir the mixture under 25 ° of C 6 hours, gains are made to leave standstill 24 hours, and filtering supernatant, the pH of gained filtrate is preferably 3 to 7, and be more preferably 3 to 6.With regard to resistance to white rust, the pH within the scope of this is preferred.
azole compounds (Dc)
Azole compounds has the heterocycle five-membered ring containing more than one nitrogen-atoms.
The example of azole compounds comprises the compound with groups such as thiazole, pyrazoles, triazole, thiadiazoles, tetrazolium, BTA, imidazoles, oxazole, selenazoles, isoxazole, isothiazole, oxadiazole, oxatriazole, thiatriazole, parbendazole, indazole, benzimidazoles.
The example with the compound of thiazolyl group comprises 2-N, and N-diethyl sulfide is for benzothiazole, 2-mercaptobenzothiazole etc.
The example with the compound of pyrazole group comprises pyrazoles, 3,5-dimethyl pyrazoles, 3-methyl-5-pyrazolone, 3-amino-5-methylpyrazole etc.
The example with the compound of triazole group comprises 1,2,4-triazole, 3-amino-1,2,4-triazole, 3-sulfydryl-1,2,4-triazole, 5-amino-3-sulfydryl-1,2,4-triazole, 2,3-dihydro-3-oxo-1,2,4-triazoles etc.
The example with the compound of thiadiazoles group comprises 5-amino-2-mercapto phenyl formic-1,3,4-thiadiazoles, 2,5-dimercapto-1,3,4-thiadiazoles etc.
The example with the compound of tetrazol group comprises 5-phenyl-1,2,3,4-tetrazolium, 5-sulfydryl-1-phenyl-1,2,3,4-tetrazolium etc.
The example with the compound of BTA group comprises 1H-BTA, I-hydroxybenzotriazole (monohydrate) etc.
In above-claimed cpd, with regard to resistance to white rust, the azole compounds especially with triazole group or thiadiazoles group can be suitable for using.
In coating composition (II), with regard to the coexisting of the resistance to water of film and resistance to white rust, based on the film formative resin (A) of the hydroxyl of 100 mass parts and the total solids content of crosslinking agent (B), the amount of azole compounds (Dc) is preferably 2 mass parts to 30 mass parts, is especially preferably 3 mass parts to 20 mass parts.
Above-mentioned azole compounds (Dc) can be used with the form of two or more combinations.
In addition, with regard to the reactivity of the solubility of azole compounds (Dc) in water and azole compounds (Dc) solution and metallic plate, when adding azole compounds (Dc) of 1 mass parts in the sodium-chloride water solution to the concentration of 100 mass parts being 5 quality % under 25 ° of C, stir the mixture under 25 ° of C 6 hours, gains are made to leave standstill 24 hours under 25 ° of C, and filtering supernatant, the pH of gained filtrate is preferably 3 to 8, and is more preferably 4 to 7.With regard to resistance to white rust, the pH within the scope of this is preferred.
Can component (Da) be used to (Dc) separately or with the form of two or more mixtures.Such as, component (Db) can with component (Dc) conbined usage, or component (Da) can with component (Dc) conbined usage.
Except the film formative resin (A) of hydroxyl, crosslinking agent (B), component (Da) to (Dc) and the optional curing catalysts added, if needed, coating composition (II) can also comprise can be used in coating composition field rust resisting pigment (outside component (Da)), coloring pigment, extender pigment, ultra-violet absorber, ultra-violet stabilizer, organic solvent; With sagging inhibitor, defoamer, painting face controlling agent and other additive.The form of coating composition (II) can be any one in organic solvent type coatings composition, water-based paint compositions and powder paint compositions.
The example of coloring pigment, extender pigment, ultra-violet absorber and ultra-violet stabilizer comprise that the component example as coating composition (I) mentions those.
Ultra-violet absorber and/or ultra-violet stabilizer are joined in coating composition, inhibits the deterioration of the film formed by coating composition (II) caused by the photoconduction arriving film coated surface.Therefore, it is possible to prevent the stripping between the film that formed by coating composition (II) and lower coating film, and excellent corrosion resistance can be kept.
If needed, the above-mentioned organic solvent that mixing can mix with coating composition (II) is to improve the coating easness etc. of coating composition (II).Available organic solvent is those solvents that can dissolve or disperse the film formative resin (A) of hydroxyl, crosslinking agent (B) and component (Da), (Db) and/or (Dc).Its instantiation comprises as those mentioned by the component example of coating composition (I).These solvents can be used separately or with the form of two or more combinations.
With regard to the corrosion resistance, acid resistance, processability etc. of film, the glass transition temperature of the cured coating film using coating composition (II) to obtain is preferably 10 ° of C to 80 ° of C, and is more preferably 20 ° of C to 50 ° of C.
Be formed in the galvanized steel plain sheet of film what comprise multilayer film, the galvanized steel plain sheet being formed with film comprising the coating using coating composition (II) to be formed in the superiors has excellent resistance to white rust.The present inventor thinks that its reason is as follows.
In galvanized steel plain sheet, especially white rust may be there is in processing department and end face portion.This is caused by the generation of zinc oxide.
The generation that zinc oxide prevents white rust is converted into by stoping the zinc ion in zine plate.When using component (Da), silicate ion can more effectively produce from multilayer film, the galvanized steel plain sheet being formed with film because of the present invention has the coating that use coating composition (II) is formed in the superiors of at least one of front and back, and this coating composition (II) comprises at least one compound be selected from as in the metal silicate in silicate ion source and metal ion exchanged silica.Silicate ion and zinc ion react to produce zinc silicate (such as, ZnSiO 3and Zn 2siO 4), prevent the generation of zinc oxide thus.Therefore, the galvanized steel plain sheet being formed with film of the present invention has very excellent resistance to white rust.
When using component (Db), more effectively can produce the resin Composition with phosphoric acid (phosphate) group from multilayer film, the galvanized steel plain sheet being formed with film because of the present invention has the coating that use coating composition (II) is formed in the superiors of at least one of front and back, and this coating composition (II) is included as the film formative resin of the phosphoric acid group in phosphate ion source and/or the film formative resin of phosphate-containing group.The resin Composition of phosphoric acid (phosphate) group and zinc ion react to produce the resin Composition with trbasic zinc phosphate group, prevent the generation of zinc oxide thus.Therefore, the galvanized steel plain sheet being formed with film of the present invention has very excellent resistance to white rust.
When using component (Dc), more effectively can produce azole compounds from multilayer film, the galvanized steel plain sheet being formed with film because of the present invention has the coating that use coating composition (II) is formed in the superiors of at least one of front and back, and this coating composition (II) comprises azole compounds.Azole compounds and zinc ion react to produce chelate compound, prevent the generation of zinc oxide thus.Therefore, the galvanized steel plain sheet being formed with film of the present invention has very excellent resistance to white rust.
the galvanized steel plain sheet being formed with film of the present invention and the method forming film
The galvanized steel plain sheet being formed with film of the present invention is included in the multilayer film that the front of galvanized steel plain sheet is formed, and one or more layers film formed on the back side.Can by forming the coating be made up of coating composition (I) on the bottom of at least one of front and back, and in the superiors of at least one of front and back, form the coating that is made up of coating composition (II) and obtain this plate.
Such as, multilayer film can be formed by the method comprised the following steps on the front of galvanized steel plain sheet, and one or more layers film can be formed on the back side:
Coating composition (I) is coated on the bottom of at least one of the front and back of galvanized steel plain sheet;
Solidify the film obtained by coating coating composition (I);
Coating composition (II) is coated in the superiors of at least one of front and back; And
Solidify the film obtained by coating coating composition (II).
In galvanized steel plain sheet, the Zn content in coating is more than 10 quality %.The example of galvanized steel plain sheet comprises galvanized steel material, the galvanized steel plain sheet that the galvanized steel plain sheet of such as melting, electrolysis the produce ,/zinc alloy steel plate of aluminizing (such as, " Galfan " (registration mark)) containing about 5% aluminium in the alloy and the profiled part be made up of galvanized steel; Galvanized alloy Steel material, such as plating iron/zinc alloy steel plate (plating iron zinc steel plate (galvannealed steel sheet)), aluminize/zinc alloy steel plate (such as, in the alloy containing the hot-dip aluminizing zincium steel plate (Galvalume steel sheet) of about 55% aluminium "; with " Galfan " in the alloy containing about 5% aluminium), and the profiled part be made up of galvanized alloy steel.Chemical conversion treatment can be carried out in their surface.The example of chemical conversion treatment comprises phosphate treated, such as trbasic zinc phosphate process and ferric phosphate process; Use the complex oxide film process of zirconates etc.; Chromium phosphate process, chromate process etc.
Be formed in the galvanized steel plain sheet of film of the present invention, first, coating composition (I) is coated on the front and back of galvanized steel plain sheet at least one on to form bottom coating.Coating composition (I) all can be coated on the front and back.With regard to the exterior durability etc. of the steel plate of coating, when coating composition (I) is only coated on side, preferably coating composition (I) is coated on front (surface used toward the outer side).
When coating composition (I) is only coated on side, can by arbitrary (primary coat) coating composition in opposite side.The example of (primary coat) coating composition except coating composition (I) comprises the coating composition based on mylar, the coating composition based on alkyd resins, (primary coat) coating composition such as coating composition based on acrylic resin.
After formation bottom coating, if needed, except the superiors' coating, one or more layers coating can also be formed in bottom coating.Usable paint composition for the formation of one or more layers so optional coating is such as, the coating composition based on mylar, the coating composition based on alkyd resins, other coating composition arbitrarily such as coating composition based on acrylic resin.
After formation bottom coating (or form one or more layers coating further in bottom coating after), coating forms the superiors' coating.The superiors on front can be one deck.
When coating composition (II) comprises component (Da) or (Db), the galvanized steel plain sheet being formed with film preferably has the multilayer film all formed on the front and back at galvanized steel plain sheet.Therefore, in this preferred embodiment, all form bottom coating (or forming one or more layers coating further in bottom coating) on the front and back, then, the coating on each surface forms the superiors' coating.
Use coating composition (II) front and back at least one on form the superiors' coating.Coating composition (II) can be used all to form the superiors' coating on the front and back.With regard to the against weather of the surface of steel plate of coating, when using coating composition (II) only to form the superiors' coating on side, (surface used towards inner side) above forms the coating be made up of coating composition (II) preferably overleaf.
When coating composition (II) is only coated on side, arbitrary face coating combination can be used to form coating on another side.
The example of face coating combination comprises the face coating combinations such as the coating composition based on mylar, the coating composition based on alkyd resins, the coating composition based on acrylic resin, the coating composition based on the mylar of silicon modification, the coating composition based on the acrylic resin of silicon modification, the coating composition based on fluororesin.When comprise to pre-coated steel plate be applied in interior processability be regarded as particular importance time, the galvanized steel plain sheet being formed with film with processability excellent especially can be obtained by using the face coating combination based on polyester being used for high level processing.
Each above-mentioned coating can be formed by each coating composition, the then solidification using known method coating to comprise coating composition (I) and (II), described known method such as, roller coat, film flow coat method, spraying, brushing or dip coated.
In each coating procedure of formation, can by coating composition being only coated on side, then solidifying, then by coating composition in opposite side, then solidify to form coating; Or by coating composition is all coated on front and back, then solidifies two surfaces simultaneously and form coating.
The cured film thickness of each coating is not particularly limited; But the cured film thickness of the coating be made up of coating composition (II) is preferably 2 μm to 20 μm, and is more preferably 3 μm to 10 μm; The cured film thickness of the coating be made up of optional ground coating composition is preferably 2 μm to 20 μm, and is more preferably 3 μm to 7 μm; And the cured film thickness of the coating to be made up of optional face coating combination is preferably 8 μm to 30 μm, and be more preferably 10 μm to 25 μm.
When by parent material as coating composition (II) of metal silicate and/or metal ion exchanged silica (Da), the cured film thickness of the coating be made up of coating composition (I) is preferably 2 μm to 20 μm, and is more preferably 3 μm to 7 μm.When by parent material as coating composition (II) of the film formative resin (Db) of the film formative resin of phosphoric acid group and/or phosphate-containing group or azole compounds (Dc), the cured film thickness of the coating be made up of coating composition (I) is preferably 2 μm to 10 μm, and is more preferably 3 μm to 7 μm.
According to the resinous type etc. used in each coating composition, can suitably regulate the solidification of film.When curing the coating obtained by methods such as coil paintings continuously, usually carry out curing 15 to 60 seconds under base material reaches maximum temperature 160 ° of C to 250 ° of C, preferably 180 ° of C to 230 ° of C.When batch processing, can carry out curing 10 to 30 minutes under 80 ° of C to 200 ° of C.
In the solidification process of film, depend on the resinous type etc. used in the coating composition, when cross-linking reaction in the process forming film does not need heating, can according to standard method by drying at room temperature cured coating film.
As the galvanized steel plain sheet being formed with film of the present invention, such as, following two kinds of galvanized steel plain sheets being formed with film have preferred coating structure.
1. be formed with the galvanized steel plain sheet of film, it has the coating be made up of coating composition (I) formed on the bottom on front (surface used toward the outer side), and the coating be made up of coating composition (II) formed in the superiors at the contrary back side.
In above-mentioned plate 1, overleaf (towards inner side use surface) the bottom on form the coating be made up of arbitrary ground coating composition.If needed, can use arbitrary coating composition front and back at least one on further form one or more layers coating.
All formed on both surfaces bottom coating (and use arbitrary coating composition front and back at least one on further form one or more layers coating) after, the superiors are overleaf formed the coating be made up of coating composition (II), and in the superiors in front, form the coating be made up of the arbitrary face coating combination comprising coating composition (II).
In plate 1, the back side only can have the coating be made up of coating composition (II).
2. be formed with the galvanized steel plain sheet of film, it has the coating be made up of coating composition (I) all formed on the bottom of both front and backs, and the coating be made up of coating composition (II) that formed in the superiors on (surface towards inner side uses) overleaf.
In above-mentioned plate 2, form bottom film, then, if needed, can use arbitrary coating composition front and back at least one on form one or more layers coating further.
Formed on both surfaces bottom coating (with use arbitrary coating composition front and back at least one on form one or more layers coating further) after, the superiors are overleaf formed the coating be made up of coating composition (II), and in the superiors in front, form the coating be made up of the arbitrary face coating combination comprising coating composition (II).
In more detail the present invention is described referring to preparation example, embodiment and comparative example.But, the present invention is not limited thereto.In each example, unless otherwise noted, " part " and " % " all represents based on quality.The thickness of film is based on cured coating film.
Embodiment
mylar prepares 1
The synthesis of preparation example a1: mylar Aa1 solution
The raw material mixture shown below is placed in the reaction vessel being equipped with agitator, thermometer, reflux condenser etc., and was heated to 230 ° of C from 160 ° of C in 3 hours.Distill out produced water by rectifying column, and products therefrom is kept 1 hour under 230 ° of C.After this, add dimethylbenzene wherein, dewater under the backflow of dimethylbenzene under 230 ° of C, and carry out esterification.
Ethylene glycol: 0.9mol
Neopentyl glycol: 0.1mol
M-phthalic acid: 0.95mol
When acid number reaches about 0, cooling products therefrom to 140 ° C also keeps 2 hours.After cooling, add Swasol 1500 (high boiling aromatic petroleum solvents is produced by MaruzenPetrochemical Co., Ltd.) wherein to obtain the mylar Aa1 solution that solids content is 35% thus.The number-average molecular weight of the resin obtained is 3,800, and glass transition temperature is 45 ° of C, and hydroxyl value is 30mg KOH/g, and acid number is about 0mg KOH/g.
phenolic resins prepares 1
Preparation example a2: first rank novolac type phenolic resin Ba1 solution
The bisphenol-A of 100 parts, 37% formalin of 178 parts and 1 part of NaOH are placed in reaction vessel, and carry out reaction 3 hours at 60 ° of C.After this, under reduced pressure product is dewatered 1 hour under 50 ° of C.One after the other add 100 parts of n-butanols and 3 parts of phosphoric acid wherein, and under 110 ° of C to 120 ° of C, carry out reaction 2 hours.After having reacted, filter gained solution, and the sodium phosphate that filtering produces, obtain the first rank novolac type phenolic resin Ba1 solution that solids content is 50%.The number-average molecular weight of gained resin is 880, and each benzene nucleus on average has 0.4 methylol and 1.0 alkoxy methyls.
coating composition (I) prepares 1
Preparation example a3
By 90 parts of Epikote#1009 (by Japan Epoxy Resin Co., Ltd. produce, bisphenol A type epoxy resin, the resin of hydroxyl) be dissolved in the mixed solvent 1 (comprising cyclohexanone/ethylene glycol monobutyl ether/Solvesso 150 (being produced by Esso Sekiyu K.K., high boiling aromatic hydrocarbon solvent)=3/1/1 (mass ratio)) of 135 parts to obtain epoxy resin solution.Then, 225 parts of these epoxy resin solutions and 20 parts of vanadic anhydrides, 20 parts of calcium phosphate, 20 parts of calcium silicates, 20 parts of titanium dioxide, 20 parts of barium monoxide and appropriate mixed solvent 2 (comprising Solvesso 150 (being produced by EssoSekiyu K.K., high boiling aromatic hydrocarbon solvent)/cyclohexanone=1/1 (mass ratio)) are mixed.Then, pigment dispersion is carried out until particle (the coarse grained particle diameter of pigment) becomes less than 20 μm.After this, the Desmodur BL 3175 adding 13.3 parts (solids contents: 10 parts) in this dispersion (is produced by Sumika Bayer Urethane Co., Ltd.; The HDI isocyanuric acid ester type polyisocyanate compounds solution of methyl ethyl ketone oxime-end-blocking; Solids content: about 75%) and the Takenate TK-1 of 1 part (solids content: 0.1 part) (prepared by Takeda Pharmaceutical CompanyLimited; Based on the end-capping reagent dissociation catalyst of organotin; About 10%) and Homogeneous phase mixing solids content:.Add aforesaid mixed solvent 2 wherein further with adjusting viscosity extremely about 80 seconds (at 25 ° of C, Ford No. 4 cups), obtain coating composition (I-1a) thus.
Preparation example a4 to a10
To obtain coating composition (I-2a) to (I-8a) with the same way that describes in preparation example a3, except such as below shown in table 1, change the hydroxy-containing resin, crosslinking agent, rust resisting pigment, other pigment and the catalyst that use in preparation example a3.The amount of the component that table 1 shows is expressed as solids content in mass.
" note " of table 1 and 2 displays refers to following.
(note 1) Cymel 303: produced by Nihon Cytec Industries Inc., trade name, methyl-etherified melmac.
(note 2) K-White G105: trade name, is produced by TAYCA Co., Ltd., the aluminium dihydrogen tripolyphosphate of magnesia process.
(note 3) Shieldex C303: produced by W.R.Grace & Co., trade name, calcium ion-exchanged silica
(note 4) Co ion-exchange silica: cobalt ions exchanges silica, (is produced by Fuji Silysia Chemical Ltd. by the Sylysia 710 of 10 mass parts; Trade name; Silica dioxide granule; Oil absorption: about 105mL/100g) to stir and 10, the concentration of 000 mass parts is mix 5 hours in the cobalt chloride solution of 5 quality %, and then filtering mixt is to collect solid content, thoroughly to wash with water and dry, acquisition Co ion-exchange silica thus.
(note 5) Nacure 5225: produced by King Industries, Inc., trade name, the DBSA of amine neutralization.
(note 6) Mg ion-exchange silica: magnesium ion exchanges silica, (is produced by Fuji Silysia Chemical Ltd. by the Sylysia 710 of 10 mass parts; Trade name; Silica dioxide granule; Oil absorption: about 105mL/100g) to stir and 10, the concentration of 000 mass parts is mix 5 hours in the magnesium fluoride aqueous solution of 5 quality %, and then filtering mixt is to collect solid content, thoroughly to wash with water and dry, acquisition Mg ion-exchange silica thus.
The coating composition (I-8a) comprising known chromium rust resisting pigment serves as reference example.
Table 1
coating composition (II) prepares 1
Preparation example a11
By 15 parts of calcium silicates, 30 parts of titanium dioxide, 40 parts of barium monoxide and appropriate mixed solvent 2 (with use in preparation example a3 identical) mix with 214.3 parts of (the resin solid contents of 75 parts) mylar Aa1 solution produced in preparation example a1.Then, pigment dispersion is carried out until particle (the coarse grained particle diameter of pigment) becomes less than 20 μm.
Thereafter, in dispersions obtained, 25 parts of Cymel 303 (note 1) are added and Homogeneous phase mixing.Nacure 5225 (the note 6 of 3 parts (solids contents: 1 part) is added in this mixture, see above) and aforesaid mixed solvent 2 with adjusting viscosity to about 80 seconds (at 25 ° of C, Ford No. 4 cups), obtain coating composition (II-1a) thus.
Preparation example a12 to a20
To obtain coating composition (II-2a) to (II-10a) with the same way that describes in preparation example a11, except as shown in table 2, change the hydroxy-containing resin, crosslinking agent, compound (Da), rust resisting pigment, other pigment and the catalyst that use in preparation example a11.In table 2, the amount of the component of display is expressed as solids content in mass.
Table 2 also show by being 5 quality % to the concentration of 100 mass parts and temperature is the compound (Da) added in the sodium-chloride water solution of 25 ° of C in each coating composition (II) of 1 part, stir the mixture under 25 ° of C 6 hours, under 25 ° of C, make gained mixture leave standstill 24 hours, and filtering supernatant and the pH value (pH of compound (Da) solution) of filtrate that obtains.
Coating composition (II-8a) and (II-9a) serve as comparative example.
Coating composition (II-10a) containing known chromium rust resisting pigment serves as reference example.
Table 2
coating composition (III) prepares 1
Preparation example a21
By 30 parts of titanium dioxide, 40 parts of barium monoxide and appropriate mixed solvent 2 (with use in preparation example a3 identical) mix with 214.3 parts of mylar Aa1 solution prepared in preparation example a1 (the resin solid contents of 75 parts).Then, pigment dispersion is carried out until particle (the coarse grained particle diameter of pigment) becomes less than 20 μm.
Thereafter, in dispersions obtained, 25 parts of Cymel 303 (note 1) are added and Homogeneous phase mixing.Nacure 5225 (the note 6 of 3 parts (solids contents: 1 part) is added in this mixture, see above) and aforesaid mixed solvent 2 with adjusting viscosity to about 80 seconds (at 25 ° of C, Ford No. 4 cups), obtain coating composition (III-1a) thus.
the galvanized steel plain sheet being formed with film prepares 1
Embodiment a1
Bar coater is used the coating composition obtained in preparation example a3 (I-1a) to be coated on the hot-dip aluminizing zincium steel plate (plate thickness: 0.4mm of chemical conversion treatment; Plate golding aluminium zinc alloy steel plate; Contain the aluminium of about 55% in the alloy; Alloy coat weight: 150g/m 2) upper be 5 μm to film thickness time dry, and cure 30 seconds in the mode making base material reach the maximum temperature of 180 ° of C, form the film as bottom on the back side thus.When the coating composition obtained in preparation example a3 (I-1a) is coated on extremely dry on the surface of steel plate (front) in the surface of steel plate with the film as bottom (back side) opposition side by use bar coater, film thickness is 5 μm, and cure 40 seconds in the mode making base material reach the maximum temperature of 220 ° of C, form the film as the bottom on front thus.
After this, on the film formed with underlying form using bar coater to be coated on by the coating composition obtained in preparation example a10 (II-1a) on the back side to film thickness time dry be 10 μm, and cure 30 seconds in the mode making base material reach the maximum temperature of 200 ° of C, form the film as upper strata on the back side thus.
After cooling, bar coater is used (to be produced by Kansai PaintCo., Ltd. by KP カ ラ ー 1580B40; Trade name; Polyester face coating combination; Blue; The glass transition temperature of cured coating film: about 70 ° of C) be coated on front the film formed with underlying form on to film thickness time dry be 15 μm, and cure 40 seconds in the mode making base material reach the maximum temperature of 220 ° of C, obtain the galvanized steel plain sheet No.1a being formed with film thus.
Embodiment a2 to a17, comparative example a1 and a2, and reference example a1
To obtain with the same way that describes in embodiment a1 the galvanized steel plain sheet 2a to 20a being formed with film, except as shown in table 3, change the coating composition used on the front and back in embodiment a1.
In table 3, with the composition that the composition that letter " X " represents is for forming each layer on front or the back side.
film performance test 1
Use the galvanized steel plain sheet 1a to 20a being formed with film obtained in embodiment a1 to a17, comparative example a1 to a2 and reference example a1 as test board, implement film performance test according to following experimental methods 1.Table 3 below shows result of the test.
test method 1
The preparation of test sample
Each breadboard is cut into and is of a size of 6cm x 12cm, when making the frontal towards film, in the face side that the burr formed at the edge part of long side is present in edge on the right and in the rear side of on the left side edge.The back of cutting blade is used to be formed to arrive at the front center part place of the breadboard of each cutting the narrow angle of substrate to be 30 degree and the line width crosscut that is 0.5mm.
Each breadboard is made to carry out the combination corrosion test (CCT:JIS K5621) of 200 circulations, and according to following standard evaluation extent of corrosion.
The outward appearance of the rust of edge: carry out visual observation according to following standard:
A: almost do not observe white rust
B: similar with the reference example comprising chromium
C: observe a small amount of white rust
D: observe obvious white rust or a small amount of white rust and red rust
The evaluation of the foaming of edge: the mean value evaluation below based on the width of the foaming from right hand edge or left hand edge development at front or back side place is bubbled:
A: be less than 5mm
More than B:5mm is also less than 10mm
More than C:10mm is also less than 20mm
D: be greater than 20mm
Cutting part: according to following standard, based at cutting width be 0.5mm substrate exposed portion on white rust length ratio and stride across the width that cutting part extends to the foaming of its both sides and evaluate cutting part:
A: be less than 50% and the width that bubbles is less than 3mm in the ratio of the white rust length at substrate exposed portion place
B: be more than 50% and the width that bubbles is less than 3mm at the white rust length ratio at substrate exposed portion place, or be less than 50% and the width that bubbles is more than 3mm and is less than 5mm in the ratio of the white rust length at substrate exposed portion place
C: be more than 50% and the width that bubbles is more than 5mm and is less than 10mm in the ratio of the white rust length at substrate exposed portion place
D: be more than 50% and the width that bubbles is more than 10mm in the ratio of the white rust length at substrate exposed portion place
Carry out humidity resistance test (at 50 ° of C, relative humidity is 98%, 500 hours), and according to following standard evaluation extent of corrosion:
The outward appearance of edge's rust: carry out visual observation according to following standard:
A: almost do not observe white rust
B: similar with the reference example comprising chromium
C: observe a small amount of white rust
D: observe obvious white rust or a small amount of white rust and red rust
The evaluation that edge bubbles: the maximum evaluation below based on the width of the foaming from right hand edge or left hand edge development at front or back side place is bubbled:
A: be less than 2mm
More than B:2mm is also less than 4mm
More than C:4mm is also less than 7mm
D: be greater than 7mm
Overall merit: be importantly that processing department and end face portion all show resistance to white rust in the galvanized steel plain sheet being formed with film.Therefore overall merit is carried out according to following standard:
A: outward appearance, the outward appearance of edge's foaming and the evaluation result of cutting part that the edge implemented after completing above-mentioned combination corrosion test becomes rusty, and the evaluation result of the outward appearance of edge's rust implemented after completing above-mentioned humidity resistance test and the outward appearance of edge's foaming is all A or B, and at least one is A.
B: above-mentioned five is all B.
C: above-mentioned five is all A, B or C, and at least one is C.
At least one of D: above-mentioned five is D.
Table 3
mylar prepares 2
The synthesis of preparation example b1: mylar Ab1 solution
The mylar Aa1 obtained in preparation example a1 is used as mylar Ab1 in the examples below that.
phenolic resins prepares 2
Preparation embodiment b2: the preparation of first rank novolac type phenolic resin Bb1 solution
The first rank novolac type phenolic resin Ba1 obtained in preparation example a2 is used as first rank novolac type phenolic resin Bb1 in the examples below that.
the resin-made of phosphoric acid (salt) group is for 1
Preparation example b3: the preparation of the acrylic resin Db1 of phosphoric acid group
100 parts of butanols are placed in reaction vessel, the temperature in reaction vessel are remained on 110 ° of C simultaneously, in 3 hours, drip the mixture with following composition wherein, wherein in advance by mixing such as monomer starting material.
Styrene: 50 parts
2-Ethylhexyl Methacrylate: 35 parts
GMA: 15 parts
2,2'-azodiisobutyronitrile: 3 parts
After this, add 0.5 part of 2,2'-azodiisobutyronitrile further wherein, and carry out reaction 2 hours further under 110 ° of C.Then, temperature in reaction vessel be adjusted to 80 ° of C and add orthophosphoric acid and the 10.4 parts of butanols that 12.2 parts of concentration are 85% wherein gradually, and carry out reaction 1 hour until the muddiness in reaction vessel disappears, obtain the acrylic resin Db1 solution that solids content is the phosphoric acid group of 50% thus.About the acrylic resin Db1 of the phosphoric acid group of gained, acid number is 54mg KOH/g (phosphate group concentration is 0.096 equivalent/100g resin), and according to molecular weight distribution, to be the mass fraction of the component of 1, less than 000 be molecular weight that 20% (area ratio according to GPC figure calculates; Hereafter same application).
Preparation example b4: the preparation of the acrylic resin Db2 of phosphoric acid group
100 parts of butanols are placed in reaction vessel, the temperature in reaction vessel are remained on 110 ° of C simultaneously, in 3 hours, drip the mixture with following composition wherein, wherein in advance by mixing such as monomer starting material.
Styrene: 40 parts
2-Ethylhexyl Methacrylate: 30 parts
GMA: 30 parts
2,2'-azodiisobutyronitrile: 3 parts
After this, add 0.5 part of 2,2'-azodiisobutyronitrile further wherein, and carry out reaction 2 hours further at 110 ° of C.Then, temperature in reaction vessel be adjusted to 80 ° of C and add orthophosphoric acid and the 17 parts of butanols that 25 parts of concentration are 85% wherein gradually, and carry out reaction 1 hour until the muddiness in reaction vessel disappears, obtain the acrylic resin Db2 solution that solids content is the phosphoric acid group of 50% thus.About the acrylic resin Db2 of the phosphoric acid group of gained, acid number is 98mg KOH/g (phosphate group concentration is 0.17 equivalent/100g resin), and according to molecular weight distribution, molecular weight is the mass fraction of the component of 1, less than 000 is 27%.
Preparation example b5: the preparation of the acrylic resin Db3 of phosphate-containing group
Be that acrylic resin Db1 solution and 5 parts of calcium oxide grinding in mortar of the phosphoric acid group of 50% are placed in solid glass container by the solids content that 100 parts (solids contents: 50 parts) obtain in preparation example b3.Then add bead wherein, and use Skandex disperser to carry out disperseing until resin solution becomes transparent.Gained solution is made at room temperature to leave standstill 48 hours.After this, removing bead, obtains the acrylic resin Db3 solution that solids content is phosphoric acid (calcium salt) group of 53% thus.
coating composition (I) prepares 2
Preparation example b6
The coating composition (I-1a) prepared in preparation example a3 is used as coating composition (I-1b) in the examples below that.
Preparation example b7 to b13
To obtain coating composition (I-2b) to (I-8b) with the same way that describes in preparation example b6, except as shown in table 4, change the hydroxy-containing resin, crosslinking agent, rust resisting pigment, other pigment and the catalyst that use in preparation example b6.The amount of component shown in table 4 is expressed as solids content in mass.
(note) in table 4 and 5 refers to table 1 and 2 above.
The coating composition (I-8b) comprising known chromium rust resisting pigment serves as reference example.
Table 4
coating composition (II) prepares 2
Preparation example b14
By 30 parts of titanium dioxide, 40 parts of barium monoxide and appropriate mixed solvent 2 (with preparation example b6 use identical) mix with the acrylic resin Db1 solution of the phosphoric acid group prepared in the mylar Ab1 solution prepared in 214.3 parts of (75 parts of resin solid contents) preparation example b1 and 20 parts of (10 parts of resin solid contents) preparation example b3.Then, pigment dispersion is carried out until particle (the coarse grained particle diameter of pigment) becomes less than 20 μm.
After this, in dispersions obtained, 25 parts of Cymel 303 (note 1) are added and Homogeneous phase mixing.Add in this mixture the Nacure 5225 (note 6) of 3 parts (solids contents: 1 part) and appropriate aforementioned mixed solvent 2 with adjusting viscosity to about 80 seconds (under 25 ° of C, Ford No. 4 cups), obtain coating composition (II-1b) thus.
Preparation example b15 to b23
To obtain coating composition (II-2b) to (II-10b) with the same way that describes in preparation example b14, except as shown in table 5, change the hydroxy-containing resin, phosphoric acid (salt) group resin, crosslinking agent, rust resisting pigment, other pigment and the catalyst that use in preparation example b14.In table 5, the amount of the component of display is expressed as solids content in mass.
Table 5 also show by being 5 quality % to the concentration of 100 mass parts and temperature is add the resin (Db) of phosphoric acid (salt) group in each coating composition (II) of 1 part in the sodium-chloride water solution of 25 ° of C, stir the mixture under 25 ° of C 6 hours, under 25 ° of C, make gained mixture leave standstill 24 hours, and filtering supernatant and the pH value (pH of resin (Db) solution) of filtrate that obtains.
Coating composition (II-8a) and (II-9a) serve as comparative example.
Coating composition (II-10b) containing known chromium rust resisting pigment serves as reference example.
Table 5
coating composition (III) prepares 2
Preparation example b24
The coating composition (III-1a) prepared in preparation example a20 is used as coating composition (III-1b) in the examples below that.
the galvanized steel plain sheet being formed with film prepares 2
Embodiment b1
To obtain with the same way that describes in embodiment a1 the galvanized steel plain sheet 1b being formed with film, except by the coating composition obtained in preparation example b14 (II-1b) for replacing coating composition (II-1a).
Embodiment b2 to b17, comparative example b1 to b2 and reference example b1
To obtain with the same way that describes in embodiment b1 the galvanized steel plain sheet 2b to 20b being formed with film, except as shown in table 6, change the coating composition for front and back used in embodiment b1.
In table 6, be the composition for forming each layer on front or the back side with the composition that letter " X " represents.
film performance test 2
Use the galvanized steel plain sheet 1b to 20b being formed with film that embodiment b1 to b17, comparative example b1 and b2 and reference example b1 obtain as test board, to carry out film performance test with the same way that describes in test method 1 above.Table 6 shows result of the test below.
Table 6
mylar prepares 3
The synthesis of preparation example c1: mylar Ac1 solution
The mylar obtained in preparation example a1 is used as mylar Ac1 in the examples below that.
phenolic resins prepares 3
Preparation example c2: the preparation of first rank novolac type phenolic resin Bc1 solution
The first rank novolac type phenolic resin Ba1 obtained in preparation example a2 is used as first rank novolac type phenolic resin Bc1 in the examples below that.
the resin-made of phosphoric acid group is for 2
Preparation example c3: the preparation of the acrylic resin Db1 of phosphoric acid group
As the acrylic resin of phosphoric acid group, be used in the acrylic resin Db1 of the phosphoric acid group prepared in preparation example b3.
coating composition (I) prepares 3
Preparation example c4
The coating composition (I-1a) prepared in preparation example a3 is used as coating composition (I-1c) in the examples below that.
Preparation example c5 to c11
To obtain coating composition (I-2c) to (I-8c) with the same way that describes in preparation example c4, except such as below shown in table 7, change the hydroxy-containing resin, crosslinking agent, rust resisting pigment, other pigment and the catalyst that use in preparation example c4.In table 7, the amount of the component of display is expressed as solids content in mass.
(note) in table 7 and 8 refers to table 1 and 2 above.
Coating composition (I-8c) containing known chromium rust resisting pigment serves as reference example.
Table 7
coating composition (II) prepares 3
Preparation example c12
By the 3-of 10 parts amino-1,2,4-triazole, the titanium dioxide of 30 parts, the barium monoxide of 40 parts and appropriate mixed solvent 2 (used identical with preparation example c4) mix with the mylar Ac1 solution prepared in preparation example c1 of 214.3 parts (75 parts of resin solid contents).Then, pigment dispersion is carried out until particle (the coarse grained particle diameter of pigment) becomes less than 20 μm.
After this, in dispersions obtained, 25 parts of Cymel 303 (note 1) are added and Homogeneous phase mixing.Add in this mixture the Nacure 5225 (note 6) of 3 parts (solids contents: 1 part) and appropriate aforementioned mixed solvent 2 with adjusting viscosity to about 80 seconds (under 25 ° of C, Ford No. 4 cups), obtain coating composition (II-1c) thus.
Preparation example c13 to c23
To obtain coating composition (II-2c) to (II-12c) with the same way that describes in preparation example c12, except as shown in the following Table 8, change the hydroxy-containing resin, azole compounds, crosslinking agent, rust resisting pigment, other pigment and the catalyst (and optional resin adding phosphoric acid group) that use in preparation example c12.In table 8, the amount of the component of display is expressed as solids content in mass.
Table 8 also show by being 5 quality % to the concentration of 100 mass parts and temperature is the azole compounds (Dc) added in the sodium-chloride water solution of 25 ° of C in each coating composition (II) of 1 part, stir the mixture under 25 ° of C 6 hours, under 25 ° of C, make gained mixture leave standstill 24 hours, and filtering supernatant and the pH value (pH of azole compounds (Dc) solution) of filtrate that obtains.
Coating composition (II-10c) and (II-11c) serve as comparative example.
Coating composition (II-12c) containing known chromium rust resisting pigment serves as reference example.
Table 8
coating composition (III) prepares 3
Preparation example c24
The coating composition (III-1a) prepared in preparation example a20 is used as coating composition (III-1c) in the examples below that.
the galvanized steel plain sheet being formed with film prepares 3
Embodiment c1
Use bar coater that the coating composition obtained in preparation example c4 (I-1c) is coated on (plate thickness: 0.4mm on the hot-dip aluminizing zincium steel plate of chemical conversion treatment; Plate golding aluminium zinc alloy steel plate; Contain the aluminium of about 55% in the alloy; Alloy coat weight: 150g/m 2) be 5 μm to film thickness time dry, and cure 30 seconds in the mode making base material reach the maximum temperature of 180 ° of C, form the film as bottom on the back side thus.Using bar coater the coating composition obtained in preparation example c4 (I-1c) to be coated on film thickness when going up extremely dry with the surface of steel plate (front) of the surface of steel plate of the film had as bottom (back side) opposition side is 5 μm, and cure 40 seconds in the mode making base material reach the maximum temperature of 220 ° of C, form the film as the bottom on front thus.
After this, when using bar coater to be coated on by the coating composition obtained in preparation example c12 (II-1c) extremely dry on the film of underlying form formation on the back side, film thickness is 10 μm, and cure 30 seconds in the mode making base material reach the maximum temperature of 200 ° of C, form the film as upper strata on the back side thus.
After cooling, bar coater is used (to be produced by Kansai PaintCo., Ltd. by KP カ ラ ー 1580B40; Trade name; Polyester face coating combination; Blue; The glass transition temperature of cured coating film: about 70 ° of C) be coated on the film that formed as the underlying form on front to film thickness time dry be 15 μm, and cure 40 seconds in the mode making base material reach the maximum temperature of 220 ° of C, obtain the galvanized steel plain sheet 1c being formed with film thus.
Embodiment c2 to c20, comparative example c1 and c3, and reference example c1
To obtain with the same way that describes in embodiment c1 the galvanized steel plain sheet 2c to 24c being formed with film, except as shown in table 9, change the coating composition for front and back used in embodiment c1.
In table 9, be the composition for the formation of each layer on front or the back side with the composition that letter " X " represents.
film performance test 3
Use the galvanized steel plain sheet 1c to 24c being formed with film obtained in embodiment c1 to c20, comparative example c1 to c3 and reference example c1 as test board, carry out film performance test in the mode identical with test method 1 above.Following table 9 shows result of the test.
Table 9

Claims (15)

1. be formed with the galvanized steel plain sheet of film, described in be formed with film galvanized steel plain sheet in its front, there is multilayer film and at its back side, there is one or more layers film; Wherein
The bottom of at least one of described front and back is formed the coating be made up of following coating composition (I), and in the superiors of at least one of described front and back, forms the coating be made up of following coating composition (II):
coating composition (I): be the coating composition comprising the film formative resin (A) of hydroxyl, crosslinking agent (B) and rust resisting pigment (C), wherein, based on the described resin (A) of 100 mass parts and the total solids content of described crosslinking agent (B), the amount of described rust resisting pigment (C) is 10 mass parts to 150 mass parts; And
coating composition (II): be comprise the film formative resin (A) of hydroxyl and the coating composition of crosslinking agent (B); Wherein,
Described coating composition (II) also comprises at least one resin (Db) of the film formative resin of film formative resin and the phosphate-containing group being selected from phosphoric acid group, and based on the described resin (A) of 100 mass parts and the total solids content of described crosslinking agent (B), the amount of described resin (Db) is 5 mass parts to 30 mass parts; Or,
Described coating composition (II) also comprises azole compounds (Dc), and based on the described resin (A) of 100 mass parts and the total solids content of described crosslinking agent (B), the amount of described azole compounds (Dc) is 2 mass parts to 30 mass parts, and described azole compounds (Dc) is for being selected from the compound with triazole group and at least one compound had in the compound of thiadiazoles group, the wherein said compound with triazole group is for being selected from 1, 2, 4-triazole, 3-amino-1, 2, 4-triazole, 3-sulfydryl-1, 2, 4-triazole, 5-amino-3-sulfydryl-1, 2, 4-triazole, 2, 3-dihydro-3-oxo-1, 2, at least one compound in 4-triazole.
2. be formed with the galvanized steel plain sheet of film as claimed in claim 1, in the coating of wherein said galvanized steel plain sheet, Zn content is more than 10 quality %.
3. be formed with the galvanized steel plain sheet of film as claimed in claim 1, at least one material of the epoxy resin that the film formative resin (A) of wherein said hydroxyl is the mylar and hydroxyl that are selected from hydroxyl.
4. be formed with the galvanized steel plain sheet of film as claimed in claim 3, the mylar that the film formative resin (A) of the hydroxyl in wherein said coating composition (II) is hydroxyl.
5. be formed with the galvanized steel plain sheet of film as claimed in claim 1, wherein said crosslinking agent (B) is for being selected from least one crosslinking agent of amino resins, phenolic resins and polyisocyanate compounds.
6. be formed with the galvanized steel plain sheet of film as claimed in claim 5, wherein said crosslinking agent (B) comprises polyisocyanate compounds and described polyisocyanate compounds is end-blocking.
7. be formed with the galvanized steel plain sheet of film as claimed in claim 1, wherein said rust resisting pigment (C) is following combination:
(1) at least one vfanadium compound of vanadic anhydride, calcium vanadate, ammonium metavanadate and vanadic acid magnesium is selected from;
(2) silicon-containing compound; And
(3) based on the slaine of phosphoric acid.
8. be formed with the galvanized steel plain sheet of film as claimed in claim 7, the wherein said slaine based on phosphoric acid (3) for be selected from calcium phosphate, calcium monohydrogen phosphate, calcium dihydrogen phosphate and wherein metallic element be at least one material of the tripolyphosphate slaine of magnesium, aluminium, zinc or calcium.
9. be formed with the galvanized steel plain sheet of film as claimed in claim 1, wherein in described resin (Db), in molecular weight distribution, molecular weight is the mass fraction of the component of 1, less than 000 is 5 quality % to 30 quality %.
10. be formed with the galvanized steel plain sheet of film as claimed in claim 1, wherein, when adding described resin (Db) of 1 mass parts in the sodium-chloride water solution to the concentration of 100 mass parts being 5 quality % at 25 DEG C, stir the mixture at 25 DEG C 6 hours, at 25 DEG C, make gains leave standstill 24 hours, and filtering supernatant, the pH of gained filtrate is 3 to 7.
11. galvanized steel plain sheets being formed with film as claimed in claim 1, wherein said coating composition (I) also comprises at least one pigment being selected from titanium dioxide and extender pigment.
12. galvanized steel plain sheets being formed with film as claimed in claim 1, wherein said coating composition (II) also comprises at least one pigment of rust resisting pigment, titanium dioxide and the extender pigment be selected from except compound (Da), and described compound (Da) is selected from least one in metal silicate and metal ion exchanged silica.
13. galvanized steel plain sheets being formed with film as claimed in claim 7, wherein, the bottom in the described front used toward the outer side is formed the coating be made up of described coating composition (I), and in the superiors at the back side of opposition side, forms the coating be made up of described coating composition (II).
14. galvanized steel plain sheets being formed with film as claimed in claim 13, on the bottom of front and back, wherein all form the coating be made up of described coating composition (I), and in the superiors at the described back side used towards inner side, form the coating be made up of described coating composition (II).
15. form multilayer film and on the back side of described galvanized steel plain sheet, form the method for one or more layers film on the front of galvanized steel plain sheet, and described method comprises the following steps:
Following coating composition (I) is coated with on the bottom of at least one be contained in the front and back of described galvanized steel plain sheet;
Solidify the film obtained by coating composition described in application (I);
Following coating composition (II) is coated with in the superiors of at least one be contained in described front and back; And
Solidify the film obtained by coating composition described in application (II);
coating composition (I): be the coating composition comprising the film formative resin (A) of hydroxyl, crosslinking agent (B) and rust resisting pigment (C), wherein, based on the described resin (A) of 100 mass parts and the total solids content of described crosslinking agent (B), the amount of described rust resisting pigment (C) is 10 mass parts to 150 mass parts; And
coating composition (II): be comprise the film formative resin (A) of hydroxyl and the coating composition of crosslinking agent (B); Wherein
Described coating composition (II) also comprises at least one resin (Db) of the film formative resin of film formative resin and the phosphate-containing group being selected from phosphoric acid group, and, based on the described resin (A) of 100 mass parts and the total solids content of described crosslinking agent (B), the amount of described resin (Db) is 5 mass parts to 30 mass parts; Or,
Described coating composition (II) also comprises azole compounds (Dc), and based on the described resin (A) of 100 mass parts and the total solids content of described crosslinking agent (B), the amount of described azole compounds (Dc) is 2 mass parts to 30 mass parts, and described azole compounds (Dc) is for being selected from the compound with triazole group and at least one compound had in the compound of thiadiazoles group, the wherein said compound with triazole group is for being selected from 1, 2, 4-triazole, 3-amino-1, 2, 4-triazole, 3-sulfydryl-1, 2, 4-triazole, 5-amino-3-sulfydryl-1, 2, 4-triazole, 2, 3-dihydro-3-oxo-1, 2, at least one compound in 4-triazole.
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