CN102069614B - Resin coating metal plate - Google Patents
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- CN102069614B CN102069614B CN 201010528392 CN201010528392A CN102069614B CN 102069614 B CN102069614 B CN 102069614B CN 201010528392 CN201010528392 CN 201010528392 CN 201010528392 A CN201010528392 A CN 201010528392A CN 102069614 B CN102069614 B CN 102069614B
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Abstract
The invention provides a resin coating metal plate which is provided with a resin capsule ontained from a surface-modified composition; the surface-modified composition comprises an inorganic component which is composed of various colloidal silica with different surface area average particle sizes, and a resin component which is composed of olefin-alpha, beta-unsaturated carboxylic acid copolymer, alpha, beta-unsaturated carboxylic acid polymer, and acrylic acid modified epoxy resin, and also comprises a silane coupling agent with epoxy propoxy groups and a metavanadate. Based on the composition, a resin coating metal plate is obtained with both corrosion resistance and rolling-resistant formability as well as post-coating coating sealing property.
Description
Technical field
The present invention relates to the resin-coated metallic plate of a kind of roller formability and the back adaptation excellence of filming after the application.
Background technology
The hot-dip galvanized steel sheet that is used for the building materials purposes has the hot-dip galvanized steel sheet (GI material) of the pure zinc of plating on steel plate and makes the alloy galvanized steel plate (GA material) etc. of its alloying.For the GI material, make the GI material continuously by (forming speed is about 20～70m/min) between the many groups roller that forms a line, form processing successively, the formed products (roller shaping) that is processed into desirable section configuration by flat board afterwards, bare (not back application) is used for deck and lightgage steel joist etc.In addition, for the GA material, after back application calcium plumbate antirusting paint, lead-free paint or the electrocoating paint etc., be used for door or shutter etc. from the teeth outwards.
Up to now, implementing chromate in order to improve corrosion stability on the surface of GI material or GA material etc. handles.But environment in recent years consciousness strengthens, and is therefore studying and is not implementing the processing method (chromate-free processing) that chromate is handled, and is developing the resin-coated metallic plate that forms the resin coating of chromate-free at hot-dip galvanized steel sheet at present.For example, disclose a kind of resin-coated metallic plate that is provided with the resin coating that is obtained by surface treating composition for TOHKEMY 2009-61608 number, wherein, described surface treating composition contains the inorganic constituents that comprises lithium metasilicate and cataloid, with contain alkene-α, beta-unsaturated carboxylic acid copolymer and α, beta-unsaturated carboxylic acid polymer be with the resinous principle of the copolymer of Han oxazolinyl, and then also contain silane coupler and the metavanadate of glycidyl.
The resin coating of putting down in writing in the above-mentioned document is suitable for the GI material.This is because when roller is shaped, the GI material is subjected to harsh face and presses, and the ratio of the resin coating of putting down in writing in the above-mentioned document great (being about 2) can form film, therefore, in roller is shaped, can alleviate the roller damage to resin coating, be not easy to make resin coating because of with the slip of roller from GI material sur-face peeling (generation tunicle slag).In addition also because when roller is shaped, for cooling processing heat when guaranteeing lubricity, cooling fluid can be supplied with GI material surface, this cooling fluid can be used repeatedly, if peeling off from the GI material, resin coating (tunicle slag) sneaks into the cooling fluid, then the resin coating of putting down in writing in the above-mentioned document many because of inorganic constituents, precipitate in cooling fluid than great, can prevent that the tunicle slag from floating and follow cooling fluid in cooling fluid.
Its result, can prevent the generation of following unfavorable condition, namely, when use is removed cooling fluid except water cushion from the surface wiping of GI material (operation dewaters), except producing, piling up tunicle slag on the water cushion surface, friction takes place between the tunicle slag of this accumulation and the formed products surface and produce noise, or formed products can not pass with uniform translational speed and causes shape of products except the water cushion part or size is inaccurate, the yield rate variation.
On the other hand, when above-mentioned resin coating also was applied to the GA material, film adaptation or corrosion stability after the application backward were insufficient.As the inadequate reason of the adaptation of filming, can think because GA material rough surface has concavo-convex, originally utilized anchoring effect can make the adaptation excellence of filming, yet because above-mentioned resin coating has been buried the concavo-convex of GA material surface, maybe can only cover the outermost layer of GA material, thereby cause the anchoring effect of GA material to disappear.In addition, as the inadequate reason of corrosion stability, can think because can only cover the outermost layer of GA material because of above-mentioned resin coating, the bottom of recess does not form tunicle and causes zinc coating to expose, after the application of back, insert cutting knife (crosscut) at application face thus and carry out corrosion stability when test, corrode down filming.And then also there are the following problems: the space that produces because of the bottom of recess causes producing bubble (coating expansion) around the crosscut portion in above-mentioned corrosion stability test; Use has absorptive lithium metasilicate as the resin coating composition.
Summary of the invention
The present invention In view of the foregoing finishes, the objective of the invention is to, obtain a kind of chromate-free surface treating composition and be provided with the resin-coated metallic plate of the resin coating that is obtained by this surface treating composition, described surface treating composition not only possesses corrosion stability, and has both the adaptation of filming after the anti-roller formability of GI material requirement and the back application that the GA material requires.
The of the present invention resin-coated metallic plate that can solve above-mentioned problem is provided with the resin coating that is obtained by surface treating composition, it is characterized in that, described surface treating composition contain the inorganic constituents that is constituted by the different multiple cataloid of surface area average grain diameter of 60～80 mass parts and 20～40 mass parts by alkene-α, the beta-unsaturated carboxylic acid copolymer, α, the resinous principle that beta-unsaturated carboxylic acid polymer and acrylic modified epoxy resin constitute, and total amount 100 mass parts that also contain described relatively inorganic constituents and described resinous principle are the silane coupler that contains glycidoxy of 5～15 mass parts and the metavanadate of 0.5～3 mass parts.
In the present invention, described inorganic constituents contains the cataloid that the surface area average grain diameter is 4～6nm (A) and the surface area average grain diameter is the cataloid (B) of 10～20nm, and described (A) and mixing ratio (B) are that 70: 30～40: 60 (mass ratio) is preferred embodiment.
Need to prove that in this manual, the surface area average grain diameter is that the cataloid of 4～6nm refers to that the surface area particle diameter is that the cataloid of 5nm accounts for the above cataloid of 90% (preferred 95%).In addition, the surface area average grain diameter is that the cataloid of 10～20nm refers to that the surface area particle diameter is that the cataloid of 12nm accounts for the above cataloid of 90% (preferred 95%).The surface area average grain diameter generally can be measured by Sears method or BET method.In order to measure the surface area average grain diameter more accurately, the electron microscope that can measure direct particle diameter is effective.
In addition, to contain the described acrylic modified epoxy resin of 2～15 quality % be preferred embodiment to described resinous principle.
And then the surface tension of described surface treating composition is that 50dyn/cm is following, the adhesion amount of described resin coating is counted 0.2～1g/m with dry mass
2, or the metallic plate that is provided with described resin coating be that hot-dip galvanized steel sheet or alloy galvanized steel plate are preferred embodiment.
For resin-coated metallic plate of the present invention, owing to be provided with the resin coating that is obtained by the surface treating composition of stipulating, therefore, not only corrosion stability can be satisfied, and the anti-roller formability of GI material requirement, the adaptation of filming after the back application that the GA material requires can be satisfied.
The specific embodiment
Resin-coated metallic plate of the present invention is provided with the resin coating that is obtained by surface treating composition, it is characterized in that, described surface treating composition contain the inorganic constituents that is constituted by the different multiple cataloid of surface area average grain diameter of 60～80 mass parts and 20～40 mass parts by alkene-α, the beta-unsaturated carboxylic acid copolymer, α, the resinous principle that beta-unsaturated carboxylic acid polymer and acrylic modified epoxy resin constitute, and total amount 100 mass parts that also contain described relatively inorganic constituents and described resinous principle are the silane coupler that contains glycidoxy of 5～15 mass parts and the metavanadate of 0.5～3 mass parts.Below, resin-coated metallic plate of the present invention is elaborated.
Need to prove, though a lot of more than the inorganic constituents resinous principle that tunicle of the present invention contains, because in this field, be called " resin coating " mostly, so also use " resin coating " such term in the present invention.
(inorganic constituents)
In the present invention, do not use lithium metasilicate as inorganic constituents.Do not show absorptive lithium metasilicate owing to use, therefore, even after back application, crosscut are carried out in the surface of resin-coated metallic plate, carry out harsh corrosion stability tests such as the experiment of salt water resistance dipping or brine spray experiment, the adaptation variation that also can suppress to film.
＜cataloid 〉
One of feature of the present invention is to use the different multiple cataloid of surface area average grain diameter as inorganic constituents.Thus, can improve the compatibility of adhesive resin (resinous principle) and cataloid, improve the film forming (adhesion between the cataloid particle) of the resin coating that forms, but also can form fine and close tunicle.
More specifically, preferably contain surface area average grain diameter as inorganic constituents and be the cataloid (A) of 4～6nm and cataloid (B) that the surface area average grain diameter is 10～20nm and constitute, more preferably constituted by cataloid (A) and cataloid (B).
For cataloid, can infer its under corrosive environment in tunicle fault location dissolving stripping, cushioning effect or passive state tunicle by pH form the dissolving/stripping that is used for suppressing metallic plate, thus the corrosion stability of raising metallic plate.In order to give full play to these effects, it is effective using cataloid (A).On the other hand, because the surface-active height of cataloid (A), if so only use cataloid (A), then often the liquid of surface treating composition stability is understood time dependent variation (tackify in about 48 hours), maybe can not form fine and close tunicle, exist the containing ratio that improves the inorganic constituents in the resin coating but can not increase the problem of the proportion of resin coating.Therefore, the inventor etc. concentrate on studies, found that if use the cataloid (B) that surface-active is little, the surface area average grain diameter is 10～20nm simultaneously, then can not make the stable containing ratio that reduces and can improve inorganic constituents of liquid of surface treating composition.Need to prove that the surface area average grain diameter of the cataloid in this specification refers to: when the surface area average grain diameter is 1～10nm left and right sides, use the value of measuring by the Sears method; When the surface area average grain diameter is 10～100nm left and right sides, use the value of measuring by the BET method, or the nominal value of in producer's brochure, putting down in writing.
The mixing ratio of cataloid (A) and cataloid (B) is preferably 70: 30～40: 60 by quality ratio, more preferably 65: 35～45: 55.When the mass ratio of cataloid (A) surpasses 70, tend to make the compatibility variation of itself and resinous principle, the liquid bad stability of surface treating composition, and can not form even, fine and close tunicle.The exposed corrosion stability of resin-coated metallic plate and the back adaptation variation of filming after the application thereupon.When the mass ratio of cataloid (A) is lower than 40, may make it under corrosive environment, reduce exposed corrosion stability variation at the Si ionic weight of tunicle defective part dissolving stripping.
Cataloid has commercially available product, and can exemplify for example is " Snowtex (registration mark) XS " of the daily output chemical industrial company manufacturing of 4～6nm as the surface area average grain diameter.In addition, be the commercially available product of 10～20nm as the surface area average grain diameter, can exemplify: be " Snowtex (registration mark) 40 ", " Snowtex (registration mark) N " that make of daily output chemical industrial company, " Snowtex (registration mark) SS ", " Snowtex (registration mark) O " etc. equally; " ADELAIDE (registration mark) AT-30 " that ADEKA company makes, " ADELAIDE (registration mark) AT-30A " etc.When the employed surface treating composition of formation resin coating is water system, disperse well in order to make cataloid, the pH that preferably takes all factors into consideration surface treating composition selects the kind of cataloid.
For the inorganic constituents that is constituted by above-mentioned cataloid, in total amount 100 mass parts of itself and resinous principle described later, account for 60～80 mass parts.The film forming of the resin coating that the surface treating composition of inorganic constituents amount in this scope forms is good, therefore is not easy to take place tunicle and peels off, and can improve the anti-roller formability of resin-coated metallic plate.In addition, the surface tension of surface treating composition reduces (it is following to be preferably 50dyn/cm), surface treating composition is immersed in the surface (recess) of the GA material of rough surface, wettability difference, and therefore the matsurface formation resin coating along the GA material also can improve corrosion stability or the adaptation of filming.
When the inorganic constituents amount surpasses 80 mass parts, because the resinous principle deficiency so the film forming of the tunicle that forms is insufficient, can not form normal tunicle.Its result tends to make that barrier effect under the corrosive environment also reduces, the corrosion stability variation.In addition, that tunicle becomes is too hard and frangible, produce the crack, and the generation tunicle is peeled off easily when roller is shaped.And then, (be about 66～73dyn/cm) because the surface tension of cataloid (amorphous silica particles is dispersed in and forms glue in the water) is higher, when the inorganic constituents amount surpasses 80 mass parts, tend to make the surface tension of surface treating composition to become big, with the wettability of the metallic plate that forms resin coating also variation, be difficult to evenly form pellicular tunica.The jog that particularly is difficult on GA material surface forms evenly and tunicle as thin as a wafer, and therefore, the adaptation of filming and exposed corrosion stability reduce.
When the amount of inorganic constituents than 60 mass parts also after a little while, tend to make the corrosion stability of the resin-coated metallic plate that obtains insufficient.In addition, the hardness deficiency of tunicle, and, because how the proportion of tunicle does not increase, so be difficult to make the resin coating filming, tunicle take place when roller is shaped easily peel off.And then, because the proportion of resin coating does not increase, therefore, the tunicle slag is precipitated in the cooling fluid receiving slit, suppress it in the effect deficiency except the water cushion surface sediment, the result tends to make operability and article shape to worsen.In addition, be lower than the surface treating composition of 60 mass parts in the amount of using inorganic constituents when metallic plate (particularly GA material) forms resin coating, the containing ratio of resinous principle increases, film forming improves, but because the Si ion stripping quantity that suppresses to corrode reduces, so (electrodeposited coating interface) begins corrosion (corrosion down of filming), the adaptation variation of filming after the result tends to make after the application between resin coating and metal sheet surface, in the corrosion resistance test after the application of back, produce bubble around the crosscut portion.
In the present invention, in total amount 100 mass parts of inorganic constituents and resinous principle, inorganic constituents is 65～75 mass parts more preferably.At this moment, cataloid (A) and mixing ratio (B) are preferably 50: 50 (mass ratio), and can making particularly, exposed corrosion stability or the adaptation of filming of GA material reach good level.
(resinous principle)
For the surface treating composition that uses among the present invention, except containing above-mentioned inorganic constituents, also contain by alkene-α, the beta-unsaturated carboxylic acid copolymer (below be sometimes referred to as " alkene-acid copolymer ".) and α, the resinous principle that beta-unsaturated carboxylic acid polymer (below be sometimes referred to as " carboxylic acid polyalcohol ") and acrylic modified epoxy resin constitute.
By forming resin coating by containing both surface treating compositions of alkene-acid copolymer and carboxylic acid polyalcohol, can improve the corrosion stability of the resin-coated metallic plate that obtains.Its accurate mechanism is still indeterminate, can be speculated as: by using the two, can form fine and close resin coating, can suppress water effectively and oxygen sees through.
Need to prove, " alkene-acid copolymer " among the present invention refers to alkene and α, and the copolymer of beta-unsaturated carboxylic acid, the formation unit that comes from alkene account in copolymer more than the 50 quality % (namely, come from α, the formation unit of beta-unsaturated carboxylic acid is that 50 quality % are following).In addition, " carboxylic acid polyalcohol " refers to α, and beta-unsaturated carboxylic acid is the polymer (also comprising copolymer) that monomer obtains, and comes from α, and the formation unit of beta-unsaturated carboxylic acid accounts in polymer more than the 90 quality %.In addition, in " α, beta-unsaturated carboxylic acid ", also comprise " α, the beta-unsaturated carboxylic acid salt " that forms with a part of carboxyl with in the nertralizer described later.
＜alkene-acid copolymer 〉
Alkene-the acid copolymer that uses among the present invention can be by making alkene and α with known method, and the beta-unsaturated carboxylic acid copolymerization is made, and commercially available product is arranged.In the present invention, can use alkene-acid copolymer more than a kind or 2 kinds.
For can being not particularly limited optimal ethylene, propylene etc., more preferably ethene for the manufacture of the alkene of alkene-acid copolymer.As alkene-acid copolymer, alkene constitutes the formation unit that the unit can use the formation unit that only comes from a kind of alkene or come from the alkene more than 2 kinds.
For can be for the manufacture of the α of alkene-acid copolymer, beta-unsaturated carboxylic acid also be not particularly limited, and for example can exemplify: monocarboxylic acids such as acrylic acid, methacrylic acid, butenoic acid, methacrylate; Dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid etc.Wherein, preferred acrylic acid.As alkene-acid copolymer, α, the formation unit of beta-unsaturated carboxylic acid can use and only come from a kind of α, and the formation unit of beta-unsaturated carboxylic acid or use come from the α more than 2 kinds, the formation unit of beta-unsaturated carboxylic acid.
For the alkene-acid copolymer that uses among the present invention, can not contain the formation unit that comes from other monomers to bringing in the dysgenic scope as corrosion stability of effect of the present invention etc. yet.In alkene-acid copolymer, the formation quantity of units that comes from other monomers be preferably 10 quality % following, more preferably below the 5 quality %, only by alkene-and α, beta-unsaturated carboxylic acid constitutes most preferred alkene-acid copolymer.As preferred alkene-acid copolymer, can exemplify ethylene-acrylic acid copolymer.
α in alkene-acid copolymer, beta-unsaturated carboxylic acid uses for the adaptation that improves resin coating and metallic plate, the α in the copolymer, the beta-unsaturated carboxylic acid amount is preferably more than the 5 quality %, more preferably more than the 10 quality %.If but α, beta-unsaturated carboxylic acid is excessive, and corrosion stability is reduced, therefore, and the α in the copolymer, the beta-unsaturated carboxylic acid amount is preferably below the 30 quality %, more preferably below the 25 quality %.
The matter average molecular weight (Mw) of the alkene-acid copolymer that uses among the present invention is preferably 1000～100,000, more preferably 3000～70,000, more preferably 5000～30,000 in polystyrene conversion.This Mw can measure as the GPC of standard by using polystyrene.
＜carboxylic acid polyalcohol 〉
As the carboxylic acid polyalcohol that uses among the present invention, can exemplify the α more than a kind or 2 kinds, the homopolymers of beta-unsaturated carboxylic acid or copolymer or the copolymer that itself and other monomer copolymerization is formed.Such carboxylic acid polyalcohol can also have commercially available product in addition with known method manufacturing.In the present invention, can use carboxylic acid polyalcohol more than a kind or 2 kinds.
For can be for the manufacture of the α of carboxylic acid polyalcohol, beta-unsaturated carboxylic acid can use as can be for the synthesis of the α of above-mentioned alkene-acid copolymer, beta-unsaturated carboxylic acid and α that example is crossed, beta-unsaturated carboxylic acid any.Wherein, preferred acrylic acid and maleic acid, more preferably maleic acid.
Carboxylic acid polyalcohol also can contain and comes from α, the formation unit of the monomer beyond the beta-unsaturated carboxylic acid, the formation quantity of units that comes from other monomers is below the 10 quality % in polymer, be preferably below the 5 quality %, more preferably only by α, the carboxylic acid polyalcohol that beta-unsaturated carboxylic acid constitutes.
As preferred carboxylic acid polyalcohol, for example can exemplify: polyacrylic acid, polymethylacrylic acid, acrylic acid-maleic acid, poly etc., wherein, consider from the viewpoint of the adaptation of filming, resin coating adaptation and corrosion stability, more preferably poly.By using poly, the particle diameter of the resin emulsion of generation is diminished (20～60nm), carry out the tunicle densification that film forming obtains, therefore can improve corrosion stability etc.In addition, because the carboxyl amount is many, so the adaptation of resin coating and metallic plate improves, corrosion stability also further improves thereupon.
The Mw of the carboxylic acid polyalcohol that uses among the present invention is preferably 500～30,000, more preferably 800～10,000, more preferably 900～3000, most preferably is 1000～2000 in polystyrene conversion.This Mw can measure as the GPC of standard by using polystyrene.
Alkene-acid copolymer in the surface treating composition and the containing ratio of carboxylic acid polyalcohol be 1000: 1～10: 1, be preferably 200: 1～20: 1, more preferably 100: 1～100: 3.When the containing ratio of carboxylic acid polyalcohol is too low, can't give full play to alkene-acid copolymer and carboxylic acid polyalcohol effect of Combination, on the contrary, when the containing ratio of carboxylic acid polyalcohol is excessive, in surface treating composition, alkene-acid copolymer and carboxylic acid polyalcohol are separated, can't form uniform resin coating.
＜acrylic modified epoxy resin 〉
In above-mentioned resinous principle, also contain acrylic modified epoxy resin.Up to now, method as the adaptation of filming that improves the back application, known have a following technology, namely, blocked isocyanate (temperature-sensitive crosslinking agent) as resinous principle is present in the tunicle, heat (sintering temperature) when utilizing sintering after the application of back makes the end-capping reagent disassociation of blocked isocyanate, makes the regeneration of active isocyanate base, makes tunicle and curing of coating crosslinked.But the calcium plumbate antirusting paint that uses in the building materials field of main flow as the back coating process can not use above-mentioned technology for not needing the normal dry type by thermal sintering (drying).
The inventor etc. concentrate on studies to the problems referred to above, found that, by use simultaneously under the low temperature can film forming acrylic modified epoxy resin as resinous principle, can improve the adaptation of filming of resin coating.Still indeterminate by the accurate mechanism of using acrylic modified epoxy resin to improve to film adaptation simultaneously, can be speculated as: acrylic modified epoxy resin is not to work as the adhesive of inorganic constituents (cataloid), though be helpless to improve exposed corrosion stability by the surface filming (point-like striped) at resin coating, help to improve the adaptation of filming after the application of back.Acrylic modified epoxy resin is in the reason of the surface filming of resin coating, can think the latex particle size 20～60nm owing to relative alkene-acid copolymer and carboxylic acid polyalcohol, the latex particle size of acrylic modified epoxy resin is approximately the above cause of 100nm.
The acrylic modified epoxy resin that uses among the present invention can be made by the following method, for example, the epoxy resin that contains the polymerism unsaturated group and (methyl) acrylic acid copolymer that epoxy resin and unsaturated fat acid reaction are obtained, or make epoxy resin and contain the vinyl monomer of glycidyl and the epoxy resin that contains the polymerism unsaturated group and (methyl) acrylic acid copolymer that the amine reaction obtains.
Particularly aqueous acrylic modified epoxy resin has commercially available product, for example can exemplify: " MODEPICS (registration mark) 301 ", " MODEPICS (registration mark) 302 " that waste river chemical industrial company makes, " MODEPICS (registration mark) 303 ", " MODEPICS (registration mark) 304 " etc.Aforesaid propylene acid modified epoxy can use separately, also can be used in combination.
In resinous principle 100 quality %, the content of acrylic modified epoxy resin is preferably above (more preferably more than the 3 quality %) 15 quality % of 2 quality % following (more preferably 7 quality % are following).The content of acrylic modified epoxy resin can reach the adaptation of filming after the raising back application under the situation of exposing corrosion stability in the anti-roller formability of not damaging resin-coated metallic plate in above-mentioned scope.
When the containing ratio of acrylic modified epoxy resin is lower than 2 quality %, the raising effect of the adaptation of filming after not seeing after the application.In addition, when the containing ratio of acrylic modified epoxy resin surpasses 15 quality %, corrosion stability is reduced.GA material particularly, its adaptation deterioration significantly of filming, and often produce bubble.The accurate mechanism that exposed corrosion stability decline and the corrosion stability of back application and the adaptation of filming descended when the containing ratio of acrylic modified epoxy resin surpassed 15 quality % is still indeterminate, can infer because hindered the cause of alkene-acid copolymer and carboxylic acid polyalcohol latex film forming because of the excessive existence of acrylic modified epoxy resin.
＜contain the silane coupler of glycidoxy 〉
In surface treating composition of the present invention, can comprise the silane coupler (in more detail, being the silane coupler that end has glycidoxy) that contains glycidoxy.If use the silane coupler that contains glycidoxy, then can improve the adaptation of metallic plate and resin coating.In addition, consider that it also has both the effect of the adhesion of the inorganic constituents that improves in the resin coating and resinous principle, the raising effect of anti-roller formability and exposed corrosion stability is big.And then, when interpolation contains the silane coupler of glycidoxy, because the surface tension of surface treating composition descends, so can improve wettability with metallic plate, improve the coating of surface treating composition, can form uniform resin coating.In addition, surface treating composition is extracted mode (after surface treating composition is injected in metal sheet surface, squeezing the coating process of strand with squeeze roll) when recycling with spraying, also show the effect of the foaming that inhibition causes by the surfactant in the composition.
As the silane coupler that contains glycidoxy, for example can exemplify: γ-glycidoxy propyl group methyldiethoxysilane, γ-glycidoxypropyltrime,hoxysilane (manufacturing of chemical industrial company of SHIN-ETSU HANTOTAI, KBM403), γ-glycidoxy methyl dimethoxysilane etc.
Total amount 100 mass parts of relative inorganic constituents and resinous principle, the silane coupled dosage that contains glycidoxy in the surface treating composition are above (more than preferred 7 mass parts) 15 mass parts of 5 mass parts following (preferred 13 mass parts are following).When silane coupled dosage is lower than 5 mass parts, do not see the effect of the adaptation that improves metallic plate and resin coating.In addition, tend to make the adhesion of inorganic constituents in the resin coating composition and resinous principle to descend, descended by film hardness, the compactness variation of tunicle, anti-roller formability, the adaptation of filming, exposed corrosion stability descend.Surpass 15 mass parts even contain the silane coupled dosage of glycidoxy, because the inorganic constituents in the adaptation of metallic plate and resin coating raising effect and the resin coating composition and the adhesion of resinous principle improve effect and culminate, so can become the main cause that cost raises.On the contrary, tend to cause that anti-roller formability, the adaptation of filming, exposed corrosion stability descend, the liquid stability decreases of surface treating composition, thus cause gelation or cataloid precipitation.
＜metavanadate 〉
In surface treating composition of the present invention, further contain metavanadate.Metavanadate also suppresses the dissolving stripping of metallic plate equally by stripping with cataloid, the effect that improves corrosion stability is arranged.Particularly to the GA material, metavanadate can be brought into play the effect that improves exposed corrosion stability.In order to bring into play this effect effectively, total amount 100 mass parts of inorganic constituents and resinous principle use metavanadate 0.5～3 mass parts to get final product relatively.If be less than 0.5 mass parts, then exposed corrosion stability raising effect is insufficient.In addition, if addition surpasses 3 mass parts, then can find out the tendency that exposed corrosion stability descends slightly.This can infer because excessive metavanadate can suppress to contain the hydrolysis of the silane coupler of glycidoxy, though just a little can influence the adhesion of inorganic constituents and resinous principle.And have that the adaptation of filming significantly reduces, the also tendency of variation of the liquid stability of surface treating composition.The metavanadate amount is 0.7～1.5 mass parts more preferably.Need to prove that the optimised quantity of this metavanadate is V element conversion amount.
As metavanadate, for example can exemplify: sodium metavanadate (NaVO
3), ammonium metavanadate (NH
4VO
3), potassium metavanadate (KVO
3) etc.These metavanadates can use separately, also can be used in combination.These metavanadates have commercially available product, can easily obtain.
＜other composition 〉
Surface treating composition of the present invention can also further comprise the compound that contains the carbonization di-imidogen.Carboxyl reaction in carbodiimide-based and alkene-acid copolymer and the carboxylic acid polyalcohol can reduce carboxyl amount, raising alkali resistance in the resin coating.In the present invention, can use the compound that contains the carbonization di-imidogen more than a kind or 2 kinds.
For the compound that contains the carbonization di-imidogen, can be by in the presence of the carbodiimides catalyst, isocyanates being heated to make, described isocyanates for example comprises: hexamethylene diisocyanate (HDI), xyxylene vulcabond (XDI), hydrogenation of benzene dimethyl vulcabond (HXDI), 4,4-'-diphenylmethane diisocyanate (MDI) or toluene di-isocyanate(TDI) (TDI) etc., but also can make it become water-based (water-soluble, water and milk voltinism or water dispersible) by modification.When surface treating composition is water system, the compound that contains the carbonization di-imidogen of preferred water-based.And contain the compound of a plurality of carbodiimide-baseds in preferred 1 molecule.When containing a plurality of carbodiimide-based in 1 molecule, by with resinous principle in the cross-linking reaction of carboxyl, can further improve exposed corrosion stability etc.
The compound that contains the carbonization di-imidogen as commercially available for example can exemplify: N, N-dicyclohexyl carbodiimide, N, N-diisopropyl carbodiimides etc.; " Carbodilite (registration mark) " series as polycarbodiimide (polymer that contains a plurality of carbodiimide-baseds in 1 molecule) that Nisshinbo company makes.As the grade of " Carbodilite (registration mark) ", " E-01 ", " E-02 " of water miscible " SV-02 ", " V-02 ", " V-02-L2 ", " V-04 " or latex type etc. are arranged.
Can be according to setting the compound amount that contains the carbonization di-imidogen as the alkene-acid copolymer of crosslinked object and the amount of carboxylic acid polyalcohol.That is, relative total amount 100 mass parts of alkene-acid copolymer and carboxylic acid polyalcohol, be preferably 0.1 mass parts above, more preferably 0.5 mass parts above, more preferably more than 8 mass parts.On the other hand, when the compound amount that contains the carbonization di-imidogen is excessive, the combined effect of alkene-acid copolymer and carboxylic acid polyalcohol is descended.And in the surface treating composition of water system, during the excessive compound that makes use carbon containing di-imidogen, can bring harmful effect to resistance to water and corrosion stability.From the viewpoint, total amount 100 mass parts of above-mentioned relatively alkene-acid copolymer and the carboxylic acid polyalcohol compound amount that contains the carbonization di-imidogen be preferably 30 mass parts following, more preferably 20 mass parts following, more preferably below 16 mass parts.
For surface treating composition of the present invention, in the scope that does not hinder effect of the present invention, can also contain paraffin, crosslinking agent, diluent, anti skinning agent, surfactant, emulsifying agent, dispersant, levelling agent, defoamer, penetrant, coalescents, dyestuff, pigment, tackifier, lubricant etc.
The surface tension of＜surface treating composition 〉
For the surface treating composition that uses among the present invention, preferably pass through the mixed proportion of suitable adjusting inorganic constituents and resinous principle (particularly, inorganic constituents: resinous principle=60: 40～80: 20) reduce the surface tension of surface treating composition, be specially 50dyn/cm following, more preferably below the 48dyn/cm.Thus, even on the surface (recess) of the GA material of rough surface, water wettability difference, surface treating composition also can immerse, and can improve the exposed corrosion stability of GA material or the adaptation of filming.Need to prove the capillary assay method aftermentioned of surface treating composition.
More than the surface treating composition that uses among the present invention is had been described in detail, below, the manufacture method of surface treating composition is described.
The manufacture method of＜surface treating composition 〉
Surface treating composition of the present invention be can be at the solvent based composition of the surface of metallic plate coating or water system composition any, consider the preferred water system: compositions from the problem of environment aspect.Surface treating composition can be prepared by the following method, that is, organic solvent (situation of solvent system: compositions) or water, preferred deionized water (situation of water system composition), cataloid, alkene-acid copolymer, carboxylic acid polyalcohol, acrylic modified epoxy resin, the silane coupler that contains glycidoxy, metavanadate, as required the compound that contains the carbonization di-imidogen or other compositions are measured mixings, stirring in accordance with regulations.
When the preparation surface treating composition, preferably in the emulsion (latex) of alkene-acid copolymer and carboxylic acid polyalcohol, add the compound that a part contains the silane coupler of glycidoxy and contains the carbonization di-imidogen, the mixture for preparing these materials adds cataloid (preferably adding in order from the little beginning of surface area average grain diameter), remaining silane coupler, metavanadate, the acrylic modified epoxy resin that contains glycidoxy therein successively.If added metavanadate contain the silane coupler of glycidoxy in interpolation before, tend to suppress the hydrolysis of silane coupler, hinder the effect of silane coupler.In addition, the preferred silane coupler that contains glycidoxy that adds at twice as mentioned above.This is that its result makes the resin coating densification, helps to improve corrosion stability because earlier the silane coupler that adds makes the latex particle miniaturization, and the silane coupler that add the back helps to guarantee with the adaptation of metallic plate and improves by membrane property.Need to prove that total amount 100 mass parts of the relative alkene-acid copolymer of amount of the silane coupler that adds and carboxylic acid polyalcohol are preferably above (more preferably more than 2 mass parts) 10 mass parts of 0.1 mass parts following (more preferably 7 mass parts are following) earlier.In addition, the amount of the silane coupler of back interpolation as mentioned above.
When stirring mentioned component, can heat.When particularly in the presence of carboxylic acid polyalcohol, alkene-acid copolymer being carried out emulsification, preferably heat.
When making the surface treating composition of water system, preferably make the alkene-acid copolymer emulsification as the principal component of resinous principle.For alkene-acid copolymer, can make its emulsification by using the carboxyl in emulsifying agent or the neutralized copolymer.When using emulsifying agent, the average grain diameter of the water based emulsion of alkene-acid copolymer is diminished, can improve the density of film forming and resin coating correspondingly etc.
Wherein, in preferred and the method for carrying out emulsification of the carboxyl in alkene-acid copolymer.This be because by in and carboxyl carry out emulsification, can reduce the consumption of emulsifying agent or not use emulsifying agent, thereby can reduce or eliminate emulsifying agent to the harmful effect of resistance to water and the corrosion stability of resin coating.In and during the carboxyl in alkene-acid copolymer, preferred carboxyl relatively uses about preferred 0.5～0.95 equivalent, the more preferably alkali about 0.6～0.8 equivalent.When neutralization is spent after a little while, emulsibility does not have to improve substantially, on the other hand, spends when big when neutralization, tends to make the viscosity of the composition that contains alkene-acid copolymer to become too high.
Alkali as being used for neutralization for example can exemplify: by the hydroxide of alkalies and alkaline earth (for example NaOH, KOH, Ca (OH)
2Deng, preferred NaOH) highly basic, ammoniacal liquor, primary amine, secondary amine, the tertiary amine (preferred triethylamine) that constitute.When highly basic such as use NaOH, though emulsibility improves, the corrosion stability of resin coating is reduced.On the other hand, (preferred boiling point under atmospheric pressure is the amine below 100 ℃ to lower boiling amine; Triethylamine for example) corrosion stability of resin coating is descended.Trace it to its cause and can think, after the coating surface treatment compositions, when carrying out heat drying formation resin coating, low-boiling amine volatilization etc.But, little because the emulsibility of amine improves effect, so preferred above-mentioned highly basic and amine make up to neutralize.Best of breed is the combination of NaOH and triethylamine.When being used in combination highly basic and amine, the relative carboxyl amount of alkene-acid copolymer, the consumption of preferred highly basic is about 0.01～0.3 equivalent, the consumption of amine is about 0.4～0.8 equivalent.
When using the surface treating composition of water system, in order to reduce surface tension, to improve the wettability to metallic plate, can mix a spot of organic solvent.Organic solvent as being used for this for example can exemplify: methyl alcohol, ethanol, isopropyl alcohol, butanols, hexanol, 2-Ethylhexyl Alcohol, ethylene glycol ethyl ether, butyl glycol ether, diethylene glycol, propane diols etc.
The solid constituent of＜surface treating composition 〉
The solid constituent of the surface treating composition that uses among the present invention is not particularly limited, and cooperates to the method adjusting of metallic plate coating surface treatment compositions to get final product.The solid constituent of surface treating composition is generally about 5～20 quality %, for example, when utilizing spraying to extract method (after surface treating composition being injected in the surface of metallic plate, squeezing the coating process of strand with squeeze roll) coating, be preferably about 10～18 quality %.
The formation method of＜resin coating 〉
In the present invention, the method and the condition that form resin coating at metallic plate are not particularly limited, can be with known coating process, make resin-coated metallic plate by carrying out heat drying on the one or both sides that surface treating composition are coated on metal sheet surface.As the coating process of surface treating composition, for example can exemplify: method etc. is extracted in excellent rubbing method, the mobile rubbing method of curtain formula, rolling method, spray-on process, spraying, wherein, considers that from viewpoints such as costs method is extracted in preferred excellent rubbing method and spraying.The heat drying condition does not have special restriction yet in addition, can example: as the heat drying temperature, be generally about 50～120 ℃, be preferably about 70～100 ℃.Too high heat drying temperature can make the resin coating variation, so not preferred.
The adhesion amount of＜resin coating 〉
For the adhesion amount of the resin coating in the resin-coated metallic plate, in dry mass, be preferably 0.2～1g/m
2, 0.3～0.7g/m more preferably
2When adhesion amount is lower than 0.2g/m
2The time, be difficult to the covered metal plate surface, the anti-roller formability of the big macrolesion of meeting, the adaptation of filming, exposed corrosion stability.On the other hand, surpass 1g/m when adhesion amount
2The time, though corrosion stability is good, the tunicle amount of peeling off when being shaped because of roller increases, so the tunicle slag increases to the accumulating amount except water cushion, may become the reason that breaks down, and is not preferred.And the adaptation of can big macrolesion filming.Need to prove that resin coating of the present invention contains a lot of inorganic constituents, than great.Therefore, compare with the resin coating in the past that resinous principle is abundant, can be under the identical situation of adhesion amount filming successfully.So also help to reduce the tunicle slag.
＜metallic plate 〉
Be not particularly limited for the metallic plate that uses among the present invention, for example can exemplify: non-plating cold-rolled steel sheet, hot-dip galvanized steel sheet (GI), alloy galvanized steel plate (GA), plated steel sheet (EG), aluminium sheet and titanium plate etc.Wherein, preferably will not carry out hot-dip galvanized steel sheet (GI), alloy galvanized steel plate (GA) that chromate handles and be applied to the present invention.
Embodiment
Below, the present invention is described in detail based on embodiment.But following embodiment does not limit the present invention, and the scheme of implementing change in the scope that does not break away from aforementioned aim described later all is included in the technical scope of the present invention.
At first, the following describes the evaluation method of using in the experimental example.
(anti-roller formability)
Cut the sample of 40mm * 300mm from resin-coated metallic plate, be vertically fixed on the cupping machine, make the sample back side and flat plate mold (material: SKD11) join.Next, make the opposite face (front) of the sample that joins with this flat plate mold and have anchor clamps (semicolumn mould, the material: SKD11) join of the protuberance of tip radius R=9.1mm, along continuous straight runs applies the load of 4900N (500kgf) to anchor clamps, the scope in-draw that anchor clamps are joined with the speed of 300mm/min, at the sample back side and flat plate mold downwards.Afterwards, after making the semicolumn mould leave sample to get back to position before sliding, carry out repeatedly 9 times and above-mentioned same slide (adding up to 10 times).Afterwards, analyze the part (W that the semicolumn mould is slided repeatedly respectively with the xrf analysis device
1) and slipper (W not
0) the tunicle adhesion amount, calculate the tunicle residual rate, estimate with following standard by following formula 1.
◎: the tunicle residual rate is more than 95%
Zero: the tunicle residual rate is more than 90% and is lower than 95%
△: the tunicle residual rate is more than 80% and is lower than 90%
*: be lower than 80%
Need to prove that the computational methods of tunicle adhesion amount are to analyze the cataloid (SiO that contains in the tunicle
2) the Si element, calculate the ratio of the Si element that contains in the tunicles based on following formula 2.
C: the cataloid (SiO in the tunicle
2) ratio
(exposed corrosion stability (SST flat board))
Based on JIS Z2371, resin-coated metallic plate is implemented salt spraytest, measure white rust incidence (gross area of the area/resin-coated metallic plate of 100 * generation white rust) and reach for 5% time.Need to prove, for the exposed corrosion stability in the building materials purposes, no matter be GI material or GA material, as long as the white rust that produces in 48 hours SST elapsed time that each chromate is handled does not just have the problem in the practicality in 5%.In addition, in other purposes, as long as the GI material more than 96 hours, the GA material is more than 72 hours, and is just no problem.
(the exposed corrosion stability (flat board) in the JASO cyclic test)
Based on JIS H8502, carry out the JASO cyclic test.1 circulation is that brine spray (temperature 35 ℃ * 2 hours) → drying (35 ℃ * humidity of temperature below 30% * 4 hours) → moistening (50 ℃ * humidity of temperature more than 95% * 2 hours) (comprises transit time respectively.)。Implementing 20 all after dates, with following standard evaluation white rust incidence (gross area of the area/resin-coated metallic plate of 100 * generation white rust).
◎: the white rust incidence is lower than 5%
Zero: the white rust incidence is more than 5%～be lower than 10%
△: the white rust incidence is more than 10%～be lower than 20%
*: the white rust incidence is more than 20%
(surface tension)
Be standard with JIS K2241, use ion exchange water to prepare 23% aqueous solution of surface treating composition, at ambient temperature, use surface tension apparatus (Shimadzu Seisakusho Ltd.'s system) and as the becket of sensor, obtain the surface tension of this aqueous solution by du nouy method.
(adaptation of filming)
At first, calcium plumbate antirusting paint (Nippon Paint Co., Ltd.'s manufacturing, HERGOM CP light gray) is diluted with diluent (Nippon Paint Co., Ltd.'s manufacturing, paint thinner A), after regulating viscosity (in the 4# Ford cup 20 seconds), with atomisation pressure 39N (4kgf) resin-coated metallic plate is carried out atomized spray painting, after the slaking 12 hours, descended dry 60 minutes 80 ℃ of temperature, make the coating material of thick 35～40 μ m of coating.
＜salt spraytest 〉
Next, after the edge, the inside of coating material is implemented to seal, insert crosscut by cutting knife, be that standard is carried out salt spraytest (SST) with JIS Z2371, after 360 hours, measure the side maximum swelling amplitude from crosscut portion, estimate with following standard.
◎: expansion amplitude is lower than 1.0mm
Zero: expansion amplitude is more than the 1.0mm and is lower than 1.5mm
△: expansion amplitude is more than the 1.5mm and is lower than 2.0mm
*: expansion amplitude is more than the 2.0mm
＜salt water resistance immersion test 〉
After the edge, the inside of coating material is implemented to seal, insert crosscut by cutting knife, dipping is 96 hours in the sodium-chloride water solution (30g/L) of 23 ℃ ± 2 ℃ of fluid temperatures, washes then, then wipe the moisture on surface, implement the belt stripping test of crosscut portion immediately.For the coating material after the disbonded test, measure and peel off the width of cloth from a side maximum of crosscut portion, estimate with following standard.
◎: strips off amplitude is lower than 1.0mm
Zero: strips off amplitude is more than the 1.0mm and is lower than 1.5mm
△: strips off amplitude is more than the 1.5mm and is lower than 2.0mm
*: strips off amplitude is more than the 2.0mm
(preparation of the emulsion of alkene-acid copolymer and carboxylic acid polyalcohol (latex))
Has the agitator of being provided with, thermometer, in the autoclave of the emulsifying device of temperature controller, adding is as ethylene-acrylic acid copolymer (the Japanese Dow Chemical manufacturing of alkene-acid copolymer, Primacor (registration mark) 5990I, come from acrylic acid formation unit: 20 quality %, matter average molecular weight (Mw): 20000, melt index: 1300, acid value: 150) 200.0 mass parts, the poly aqueous solution (" nonpolar (registration mark) PMA-50W " that Nof Corp. makes as carboxylic acid polyalcohol, Mw: about 1100 (polystyrene conversion), 50 quality % product) 8.0 mass parts, triethylamine 35.5 mass parts (carboxyl of ethylene-acrylic acid copolymer is 0.63 equivalent relatively), the 48%NaOH aqueous solution 6.9 mass parts (carboxyl of ethylene-acrylic acid copolymer is 0.15 equivalent relatively), (the Harry agate changes into company and makes ready denier oil acid, HARTALL FA3) 3.5 mass parts, ion exchange water 792.6 mass parts and sealing, high-speed stirred was cooled to 30 ℃ after 3 hours under 150 ℃ and 5 atmospheric pressure.Next (stepping figure new high-tech material (former GE Toshiba organosilicon) company makes to add the silane coupler contain glycidoxy, TSL8350, γ-glycidoxypropyltrime,hoxysilane) 10.4 mass parts, compound (" Carbodilite (registration mark) SV-02 " that Nisshinbo company makes that contains the carbonization di-imidogen, polycarbodiimide, Mw:2700, solid constituent 40 quality %) 31.2 mass parts, ion exchange water 72.8 mass parts, stirred 10 minutes, and made emulsion (latex) (the about 20 quality % of solid component concentration of alkene-acid copolymer and carboxylic acid polyalcohol, be that standard is measured with JIS K6833).
(experimental example 1-1～1-10)
The preparation of＜surface treating composition 〉
In above-mentioned emulsion, (daily output chemical industrial company makes to add the cataloid that the surface area average grain diameter is 4～6nm (nominal value) (A) successively, Snowtex (registration mark) XS (solid component concentration 20%)) and the surface area average grain diameter be that (daily output chemical industrial company makes for the cataloid (B) of 10～20nm (nominal value), Snowtex (registration mark) 40 (solid component concentration 40%)), after both are fully mixed, (chemical industrial company of SHIN-ETSU HANTOTAI makes to add the silane coupler that contains glycidoxy, KBM403 (solid component concentration 100%)), (emerging chemical industrial company makes to follow the sodium metavanadate that adds as metavanadate, sodium metavanadate (solid component concentration about 66%)).In this mixture, further add acrylic modified epoxy resin (waste river chemical industrial company makes, MODEPICS (registration mark) 302 (solid component concentration 33.5%)), make surface treating composition.
Need to prove that the combined amount (or mixing ratio) of each composition during above-mentioned surface treating composition is made is as follows.
Cataloid (A) and mass ratio (B) 50: 50
The mass ratio of inorganic constituents and resinous principle (all solids composition in the above-mentioned emulsion and the combined amount of acrylic modified epoxy resin, below identical) 30: 70～95: 5
All solids composition 95 mass parts in the above-mentioned relatively emulsion of the combined amount of acrylic modified epoxy resin are 5 mass parts (being 5 quality % in the resinous principle)
Containing the relative inorganic constituents of combined amount of silane coupler of glycidoxy and total amount 100 mass parts of resinous principle is 10 mass parts
Total amount 100 mass parts of the relative inorganic constituents of the combined amount of metavanadate and resinous principle are 1 mass parts
The making of＜resin-coated metallic plate 〉
As metallic plate, use alkali degreasing hot-dip galvanized steel sheet GI material (Zn adhesion amount 45g/m
2) or alloy galvanized steel plate GA material (Zn adhesion amount 45g/m
2), be coated with machine (No.3 rod or No.4 rod) with rod and be coated with above-mentioned surface treating composition on the surface of steel plate, about 12 seconds of 90 ℃ of following heat dryings of plate temperature, making the resin coating adhesion amount was 0.5g/m
2Resin-coated metallic plate.The evaluation result of the resin-coated metallic plate that obtains is shown in table 1.
(experimental example 1-11)
The preparation of＜surface treating composition 〉
With SiO
2/ Li
2The O mol ratio is that 4.5 lithium metasilicate (" lithium metasilicate 45 " that daily output chemical industrial company makes) and surface area average grain diameter (nominal value) are that the cataloid (daily output chemical industrial company makes, Snowtex (registration mark) XS) of 4～6nm is that 90: 10 mode is mixed by quality ratio, prepares inorganic constituents.
In above-mentioned emulsion, add the inorganic constituents that obtains, after both are fully mixed, add the silane coupler (manufacturing of chemical industrial company of SHIN-ETSU HANTOTAI, KBM403, γ-glycidoxy propyl-triethoxysilicane) that contains glycidoxy, then add sodium metavanadate (manufacturing of emerging chemical industrial company, inclined to one side sodium vanadate).In this mixture, further add the copolymer that contains oxazolinyl (manufacturings of Japanese catalyst company, Epocros (registration mark) K-2030E, solid constituent 40 quality %), prepare surface treating composition.
Need to prove that the combined amount (or mixing ratio) of each composition during above-mentioned surface treating composition is made is as follows.
All solids composition in inorganic constituents and the above-mentioned emulsion is with the mixing ratio of the mixture of the copolymer of Han oxazolinyl 70: 30
All solids composition 95 mass parts in the above-mentioned relatively emulsion of the combined amount of the copolymer of Han oxazolinyl are 5 mass parts
Contain the relative inorganic constituents of combined amount of silane coupler of glycidoxy and all solids composition in the above-mentioned emulsion with total amount 100 mass parts of the mixture of the copolymer of Han oxazolinyl are 15 mass parts
All solids composition in the relative inorganic constituents of the combined amount of sodium metavanadate and the above-mentioned emulsion is with total amount 100 mass parts of the mixture of the copolymer of Han oxazolinyl are 5 mass parts
The preparation of＜resin-coated metallic plate 〉
Except the surface treating composition that uses experimental example 1-11 preparation, 1-1 operates equally with experimental example, makes resin-coated metallic plate.The evaluation result of the resin-coated metallic plate that obtains is shown in table 1.
(experimental example 2-1～2-10)
The preparation of＜surface treating composition 〉
Except the mass ratio that makes cataloid (A) and cataloid (B) changed by 100: 0～0: 100,1-3 operated equally with experimental example, makes surface treating composition.
The making of＜resin-coated metallic plate 〉
Except the surface treating composition that uses experimental example 2-1～2-10 preparation, 1-3 operates equally with experimental example, makes resin-coated metallic plate.The evaluation result of the resin-coated metallic plate that obtains is shown in table 2.
(experimental example 2-11～2-12)
Be that the cataloid (daily output chemical industrial company makes, Snowtex (registration mark) 50) of 20～30nm (nominal value) or the cataloid that the surface area average grain diameter is 40～50nm (nominal value) (daily output chemical industrial company makes, Snowtex (registration mark) 20L) replace the cataloid (B) except using the surface area average grain diameter, 2-1 operates equally with experimental example, makes surface treating composition.
The making of＜resin-coated metallic plate 〉
Except the surface treating composition that uses experimental example 2-11～2-12 making, 2-1 operates equally with experimental example, makes resin-coated metallic plate.The evaluation result of the resin-coated metallic plate that obtains is shown in table 2.
(experimental example 3-1～3-11)
The preparation of＜surface treating composition 〉
All solids composition 80～100 mass parts in the above-mentioned relatively emulsion of the combined amount that makes acrylic modified epoxy resin are that 1-3 operates equally with experimental example 0～20 mass parts (being 0～20 quality % in the resinous principle), make surface treating composition.
The making of＜resin-coated metallic plate 〉
Except the surface treating composition that uses experimental example 3-1～3-11 preparation, 1-3 operates equally with experimental example, makes resin-coated metallic plate.The evaluation result of the resin-coated metallic plate that obtains is shown in table 3.
(experimental example 4-1～4-9)
The preparation of＜surface treating composition 〉
Except total amount 100 mass parts that make the relative inorganic constituents of combined amount that contains glycidoxy de silane coupler and resinous principle were 0～20 mass parts, 1-3 operated equally with experimental example, made surface treating composition.
The making of＜resin-coated metallic plate 〉
Except the surface treating composition that uses experimental example 4-1～4-9 preparation, 1-3 operates equally with experimental example, makes resin-coated metallic plate.The evaluation result of the resin-coated metallic plate that obtains is shown in table 4.
(experimental example 5-1～5-10)
The preparation of＜surface treating composition 〉
Except total amount 100 mass parts of the relative inorganic constituents of the combined amount that makes metavanadate and resinous principle were 0～5 mass parts, 1-3 operated equally with experimental example, made surface treating composition.
The making of＜resin-coated metallic plate 〉
Except the surface treating composition that uses experimental example 5-1～5-10 preparation, 1-3 operates equally with experimental example, makes resin-coated metallic plate.The evaluation result of the resin-coated metallic plate that obtains is shown in table 5.
(experimental example 6-1～6-8)
The making of＜resin-coated metallic plate 〉
Be 0.1～1.5g/m except making the resin coating adhesion amount
2In addition and experimental example 1-3 operate equally, make resin-coated metallic plate.The evaluation result of the resin-coated metallic plate that obtains is shown in table 6.
The possibility of commercial Application
The present invention can provide the resin-coated metallic plate of the adaptation of filming after a kind of anti-roller formability that not only satisfies corrosion stability but also satisfy the requirement of GI material, the back application that the GA material requires.
Claims (7)
1. resin-coated metallic plate, it is provided with the resin coating that is obtained by surface treating composition, it is characterized in that,
Described surface treating composition contains: the inorganic constituents that is made of the different multiple cataloid of surface area average grain diameter of 60～80 mass parts, and 20～40 mass parts by alkene-α, beta-unsaturated carboxylic acid copolymer, α, the resinous principle that beta-unsaturated carboxylic acid polymer and acrylic modified epoxy resin constitute
And total amount 100 mass parts that also contain described relatively inorganic constituents and described resinous principle are the silane coupler that contains glycidoxy of 5～15 mass parts and the metavanadate of 0.5～3 mass parts.
2. resin-coated metallic plate according to claim 1, wherein, it is the cataloid B of 10～20nm that described inorganic constituents contains cataloid A and the surface area average grain diameter that the surface area average grain diameter is 4～6nm, and the mixing ratio of described cataloid A and cataloid B is 70: 30～40: 60 by quality ratio.
3. resin-coated metallic plate according to claim 1 and 2, wherein, described resinous principle contains the described acrylic modified epoxy resin of 2～15 quality %.
4. resin-coated metallic plate according to claim 1 and 2, wherein, the surface tension of described surface treating composition is below the 50dyn/cm.
5. resin-coated metallic plate according to claim 1 and 2, wherein, the adhesion amount of described resin coating is counted 0.2～1g/m with dry mass
2
6. resin-coated metallic plate according to claim 1 and 2, wherein, the described metallic plate that is provided with resin coating is hot-dip galvanized steel sheet.
7. resin-coated metallic plate according to claim 1 and 2, wherein, the described metallic plate that is provided with resin coating is alloy galvanized steel plate.
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| JP6285806B2 (en) * | 2014-06-04 | 2018-02-28 | ナブテスコ株式会社 | Drive device for upper revolving structure by hybrid drive system |
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| JP2016175257A (en) * | 2015-03-19 | 2016-10-06 | 株式会社神戸製鋼所 | Resin coated metal plate |
| JP6705680B2 (en) * | 2016-03-30 | 2020-06-03 | 株式会社神戸製鋼所 | Non-condensation type thermoplastic resin plate for adhesion of thermoplastic resin and composite member using the same |
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| TW201132802A (en) | 2011-10-01 |
| KR20110046350A (en) | 2011-05-04 |
| KR101237652B1 (en) | 2013-02-27 |
| JP2011092837A (en) | 2011-05-12 |
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